A charge reversal differentiates (p)ppGpp synthesis by monofunctional and bifunctional Rel proteins

A major regulatory mechanism evolved by microorganisms to combat stress is the regulation mediated by (p)ppGpp (the stringent response molecule), synthesized and hydrolyzed by Rel proteins. These are divided into bifunctional and monofunctional proteins based on the presence or absence of the hydrolysis activity. Although these proteins require Mg2+ for (p)ppGpp synthesis, high Mg2+ was shown to inhibit this reaction in bifunctional Rel proteins from Mycobacterium tuberculosis and Streptococcus equisimilis. This is not a characteristic feature in enzymes that use a dual metal ion mechanism, such as DNA polymerases that are known to carry out a similar pyrophosphate transfer reaction. Comparison of polymerase Polβ and RelSeq structures that share a common fold led to the proposal that the latter would follow a single metal ion mechanism. Surprisingly, in contrast to bifunctional Rel, we did not find inhibition of guanosine 5′-triphosphate, 3′-diphosphate (pppGpp) synthesis at higher Mg2+ in the monofunctional RelA from Escherichia coli. We show that a charge reversal in a conserved motif in the synthesis domains explains this contrast; an RXKD motif in the bifunctional proteins is reversed to an EXDD motif. The differential response of these proteins to Mg2+ could also be noticed in fluorescent nucleotide binding and circular dichroism experiments. In mutants where the motifs were reversed, the differential effect could also be reversed. We infer that although a catalytic Mg2+ is common to both bifunctional and monofunctional proteins, the latter would utilize an additional metal binding site formed by EXDD. This work, for the first time, brings out differences in (p)ppGpp synthesis by the two classes of Rel proteins

Core-substituted naphthalene diimides: influence of substituent conformation on strong visible absorption

Substitution of the aromatic core of naphthalene diimide (NDI) chromophores by morpholine leads to molecules with strong absorbance in the visible spectrum. The shift of absorption maxima to lower energy is determined not only by the degree of substitution but also by the relative conformation and orientation of the tertiary amine with respect to the plane of the NDI

Aggregation induced emission macromolecules: structures, properties and their supramolecular applications

Luminescence is the process of light emission by luminescent materials. In recent years, the development of luminescent materials gained a lot of attention due to their promising applications in various fields such as electroluminescent devices including organic light emitting diodes (OLEDs), organic field effect transistors (OFETs), sensors, and so on. However, these luminescent materials were suffered from the fluorescence quenching in their solid state. The conventional luminophores shows stronger light emission in the solution state and emission becomes weaker in the condensed phase i.e. in thin solid films or aggregate state. Simply, the light emissions of these traditional molecules were suffered from aggregation of molecules. This process of fluorescence quenching was referred as Aggregation Caused Quenching (ACQ). The ACQ effect of many luminogens was creating obstacles for these luminophores while applying in the real-world applications in solid state or aqueous phase, as they show aggregation in these phases. Multiple processes have been discovered including physical, chemical and engineering attempts to alleviate the problem of fluorescence quenching upon aggregation however only limited success was achieved. The development of such luminogen which will be able to show the enhanced emission upon aggregation and in the solid state was suggested the solution for emission quenching effect (ACQ) of common luminogens. Later, in 2001, the phenomenon of Aggregation Induced Emission (AIE) was reported by Tang group which is exactly opposite to the earlier ACQ effect. In this AIE process, the luminophores showed enhanced emission in the solid and aggregate state and their emission is reduced in the dilute solution studies. The 1,1,2,3,4,5-hexaphenyl-1H-silole (HPS) molecule is the first AIE gen discovered which showed turn “off” and “on” emission in the solution and solid state. It was found that the restriction of intramolecular motions including rotations and vibrations causes the molecule to be emissive in the aggregate state. The invention of AIE and understanding of its mechanism plays positive role in presenting a new platform to investigate the functionally useful luminescent materials for real world applications. The variety of luminogens (AIEgens) with high emission efficiency (quantum yield) in the condensed phase have been developed and becomes the promising candidates for many technological applications such as fluorescent sensors, OLEDs, solid lasers, fluorescence gels, biomarkers, etc. Among these AIEgens, Tetraphenylethylene (TPE) and its derivatives are extensively studied and have gained tremendous attention due to its characteristics features as compared to the rest of AIEgens. TPE is easy to synthesize, shows bright emission in the solid state and non-emissive in the solution. It has very simple, stable molecular structure and is readily accessible for structural modification. Moreover, it gives high quantum efficiency, also useful for solving the problem of ACQ effect of many common luminogen and behaves as mechanochromic luminescent material in the solid state. Considering all factors in mind, many AIE active TPE luminogens have been introduced for multiple applications such as chemo sensors, bio-probes, solid-state emitters, luminescent gel, etc. In this body of work, the synthesis of several aggregations induced emission macro-molecules especially tetraphenylethylene derivatives, their properties and various supramolecular applications such as pH sensors, multifunctional mechanochromic luminescent probe, artificial light harvesting antenna, an AIE activity of the sterically hindered system, AIE active NDIs and BHJ solar cells, have been presented. TPE derivatives have been employed as fluorescent sensors for detection of metal ions such as Cu2+, Hg2+, Ag+, Cr3+, Al3+ and so on. However, a TPE based reversible fluorescent pH sensor for a solution and live cells is rarely reported. The synthesis of TPE-pyridyl derivative and its utilization for pH detection in the solution and live cells were investigated. This derivative undergoes protonation in acidic medium and deprotonation in the basic medium which makes it a reversible probe as pH sensor. The process of reversibility of protonation and deprotonation process in a different medium is confirmed by a colour change, UV-Vis, fluorescence study and self-assembly of protonated and unprotonated species. After treating this dye in PC-3 cells, cells showed green fluorescence at acidic pH and blue at neutral and basic pH. Furthermore, the substituted derivative of Py-TPE salt has been shown the mechanochromism property in the solid state. When it was used for cellular imaging, DNA marking and cell-cycle analysis, it showed better results/performance as compared to commercially available and commonly used dyes. Photosynthesis is the vital process in plants which involves the production of chemical energy from CO2 and H2O in the presence of sunlight where LH2 complex plays an important role as it involves in the absorption, storage and transfer of light energy to the reaction centre. This natural harvesting complex has commonly explored the model in making artificial light harvesting systems where porphyrins are arranged in the ring of turbines and involves in the light transportation process. Taking advantage, the next derivative has been designed to mimic the nature using TPE and porphyrin, synthesized and utilised as an artificial light harvesting antenna. The SEM and TEM results confirm the formation of ring shaped morphology reminiscent with LH2 complex and time resolved absorption spectroscopy results confirm the absorption and energy transfer process by the derivative. So far, the developed AIE active derivatives are simple in structure, however, the AIE activity in the stearically hindered system is rarely reported. Moreover, the AIEgens with mechanochromic properties is extensively studied and widely shown the application in smart materials such as security papers, storage device, etc. However, very few TPE based derivatives have shown the mechanochromism behaviour. The HTCA, a stearically hindered AIEgen have been developed and its AIE activity, mechanochromic properties are investigated. This derivative is highly luminescent in the aggregate state, and its mechanochromic properties make it a promising candidate for smart materials applications. The well-known naphthalene diimide (NDI) is extensively studied and widely gained attention due to its electro-optical properties and applications in the numerous field. However, it severely suffered from luminescence quenching in the solid state which results in the limitation of application of NDI derivatives as luminescent materials in different areas. To convert the ACQ effect of NDIs into AIE, tetraphenylethylene have been incorporated on to the NDI core. The mono, di and tetra-substitution of TPE on NDI core converted ACQ active moiety into AIE active moiety and shown that it can used as luminescent material in the solid state. Furthermore, the application of TPE derivative in solar cell devices has been studied. TPE based four-directional, non-fullerene acceptor; 4D has been developed for solution processable BHJ device. 4D was prepared by simple reaction between Br4-TPE and DPPboronate ester using Suzuki conditions. High solubility in organic solvents, thermal stability, absorption in the visible region, red-shift in emission, and comparable energy level with P3HT makes it a promising candidate for BHJ device. The device prepared using 4D as an acceptor with P3HT (1:1.2) gives an excellent high voltage current Voc 1.18 V and recorded a PCE of 3.86%. Overall, this thesis provided the knowledge and further applications of TPE derivatives in different fields. To my knowledge, the derivatives synthesised and shown here are the first examples in the literature of their possible applications

Aggregation-induced emission of a star-shape luminogen based on cyclohexanehexone substituted with AIE active tetraphenylethene functionality

We describe a rigid star-shaped luminogen (HTCA) of cyclohexanehexone bearing six tetraphenylethene moieties, which exhibited strong aggregation-induced emission (AIE) characteristics. The twisting amplitude and steric hindrance of the TPE units were found to play a crucial role in their aggregated nano- to micro-structures. Interestingly, HTCA exhibits reversible piezofluorochromic behaviour through grinding which is reversed by treatment with solvents resulting in a cycle that can be repeated several times

Construction of a highly efficient near-IR solid emitter based on naphthalene diimide with AIE-active tetraphenylethene periphery

Tetraphenylethene-core-substituted naphthalene diimide (TTPEcNDI) shows distinct near-IR optical properties and aggregation induced emission phenomena. Furthermore, TTPEcNDI aggregated into a variety of supramolecular assembled structures via solvophobic control such as hollow spheres, bundles of fibrils and leaf-like structures with controlled dimensions. The present study can be applied to more elaborate supramolecular structures for the development of near-IR solid emitter luminescent nanomaterials for electronic applications

Solvophobic control aggregation-induced emission of tetraphenylethene-substituted naphthalene diimide via intramolecular charge transfer

Two new tetraphenylethene-core-substituted naphthalene diimides (TPE-cNDI) were synthesized through linking one and two TPE, where TPE acts both as an electron-donor for ICT and also display the characteristic of AIE effect, i.e. is non-emissive in solution but has enhanced red-emission in both the aggregated and the solid state with high quantum efficiency. Furthermore, both the derivatives self-assembled into variety of nano- to micro-structures via solvophobic control

Clathrate directed assembly of tetrapyridyl-tetraphenylethylene metal-organic frameworks

This work focuses on three 2-D MOFs based on the ligand tetrapyridyltetraphenylethylene (tppe) with the metal ions manganese(II), nickel(II) and copper(II). These networks are all highly microporous with rhomboid channels measuring similar to 14 x 17 angstrom giving approximately 49% solvent accessible void space. These voids are filled with ordered tetrachloroethylene (TCE) molecules that act as structure directing agents, and the structures remain porous even after removal of TEC molecules. The networks were characterised via single crystal X-ray diffraction, powder XRD, TGA, FTIR, fluorescence spectroscopy, and elemental analysis. Gas absorption measurements on the desolvated networks indicate that the networks are moderately selective, and their behaviour was typical of similar MOF networks. The Ni2+ based tppe-MOF exhibited greater capacity to absorb polar gases despite structural similarities to the other networks

Nanostructured charge transfer complex of CuTCNQF4 for efficient photo-removal of hexavalent chromium

The high toxicity of hexavalent chromium warrants the development of efficient catalysts that could reduce chromium into relatively non-toxic trivalent chromium species. Pristine charge transfer complexes of the MTCNQ family (M = Cu or Ag; TCNQ = 7,7,8,8-tetracyanoquinodimethane) have previously failed to catalyse the reduction of Cr6+ to Cr3+. We demonstrate that due to the outstanding electron transfer properties of one of the fluorinated derivatives of MTCNQ, i.e., 7,7,8,8-tetracyano-2,3,5,6-tetraflouroquinodimethane (CuTCNQF4), it is able to catalyse the reduction of hexavalent chromium in aqueous solution at room temperature. We further demonstrate that the semiconducting nature of these organic charge transfer complexes allows CuTCNQF4 to act as an outstanding material for the reductive photo-removal of hexavalent chromium under UV photoexcitation conditions. Such materials are likely to play an important role in photoactive electron transfer reactions