Deep Phosphoproteome Landscape of Interhemispheric Functionality of Neuroanatomical Regions of the Human Brain.

Post-translational modifications (PTMs) are one of the compulsive and predominant biological processes that regulate the diverse molecular mechanism, modulate the onset of disease, and are the reason behind the functional diversity of proteins. Despite the widespread research findings in neuroproteomics, one of the key drawbacks has been the lack of proteome-level knowledge of hemispheric lateralization. We have investigated the proteome level expression in different neuroanatomical regions under the Human Brain Proteome Project (HBPP) and developed the global interhemispheric brain proteome map (Brainprot) earlier. Furthermore, this study has extended to decipher the phosphoproteome map of human brain interhemispheric regions through high-resolution mass spectrometry. The phosphoproteomics examination of 12 unique interhemispheric neurological brain regions using Orbitrap fusion liquid chromatography with tandem mass spectrometry provided comprehensive coverage of 996 phosphoproteins, 2010 phosphopeptides, and 3567 phosphosites. Moreover, interhemispheric phosphoproteome profiling has been categorized according to synaptic ontologies and interhemispheric expression to understand the functionality. Finally, we have integrated the phosphosites data under the PhosphoMap section in the Inter-Hemispheric Brain Proteome Map Portal (https://www.brainprot.org/) for the advancement and support of the ongoing neuroproteomics research worldwide. Data is available via ProteomeXchange with the identifier PXD031188.

Visible-Light-Driven Photocatalytic CO2 Reduction to CO/CH4 Using a Metal-Organic "Soft" Coordination Polymer Gel.

The self-assembly of a well-defined and astutely designed, low-molecular weight gelator (LMWG) based linker with a suitable metal ion is a promising method for preparing photocatalytically active coordination polymer gels. Here, we report the design, synthesis, and gelation behaviour of a tetrapodal LMWG based on a porphyrin core connected to four terpyridine units (TPY-POR) through amide linkages. The self-assembly of TPY-POR LMWG with RuII ions results in a Ru-TPY-POR coordination polymer gel (CPG), with a nanoscroll morphology. Ru-TPY-POR CPG exhibits efficient CO2 photoreduction to CO (3.5 mmol g-1 h-1 ) with >99 % selectivity in the presence of triethylamine (TEA) as a sacrificial electron donor. Interestingly, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH) with TEA as the sacrificial electron donor, the 8e- /8H+ photoreduction of CO2 to CH4 is realized with >95 % selectivity (6.7 mmol g-1 h-1 ). In CPG, porphyrin acts as a photosensitizer and covalently attached [Ru(TPY)2 ]2+ acts as a catalytic center as demonstrated by femtosecond transient absorption (TA) spectroscopy. Further, combining information from the in situ DRIFT spectroscopy and DFT calculation, a possible reaction mechanism for CO2 reduction to CO and CH4 was outlined.

Bimodal Heterogeneous Functionality in Redox-Active Conjugated Microporous Polymer toward Electrocatalytic Oxygen Reduction and Photocatalytic Hydrogen Evolution.

The designing and development of heterogeneous catalysts for conversion of renewable energy to chemical energies by electrochemical as well as photochemical processes is at the forefront of energy research. In this work, two new donor-acceptor-based redox-active conjugated microporous polymers (CMPs) (TAPA-OPE-mix and TAPA-OPE-gly) are synthesized through Schiff base condensation reaction using a microwave synthesizer. Notably, the asymmetric and symmetric bola-amphiphilic nature of the OPE struts results in distinct nanostructuring and morphologies in the CMPs. Interestingly, both CMPs show impressive heterogeneous catalytic activity toward electrochemical O2 reduction and photocatalytic H2 evolution reactions, and therefore, act as bimodal electro- and photocatalytic porous organic materials. Furthermore, the redox-active property of the CMPs is exploited for in situ generation and stabilization of platinum nanoparticles (Pt), and these Pt@CMPs exhibit significantly enhanced photocatalytic activity.

A Chemodosimetric Approach for Fluorimetric Detection of Hg2+ Ions by Trinuclear Zn(II)/Cd(II) Schiff Base Complex: First Case of Intermediate Trapping in a Chemodosimetric Approach.

The present work discloses the application of two fluorescent zinc and cadmium complexes (1 and 2) for sensing of Hg(II) ions through a chemodosimetric approach. The ligand under consideration in this work is a N2O donor Schiff base ligand (E)-4-bromo-2-(((2-morpholinoethyl)imino)methyl)phenol (HL), which has been harnessed to generate complexes [Zn3L2(OAc)4] (1) and [Cd3L2(OAc)4] (2). X-ray single crystal diffraction studies unveil the trinuclear skeleton of complexes 1 and 2. Both complexes have been found to be highly fluorescent in nature. However, the quantum efficiency of Zn(II) complex (1) dominates over the Cd(II) analogue (2). The absorption and emission spectroscopic properties of the complexes have been investigated by density functional theory. Complexes 1 and 2 can detect Hg2+ ions selectively by fluorescence quenching, and it is noteworthy to mention that the mechanism of sensing is unique as well as interesting. In the presence of Hg2+ ions, complexes 1 and 2 are transformed to mononuclear mercuric intermediate complex (3) and finally to a trinuclear mercuric complex (4) by hydrolysis. We have successfully trapped the intermediate complex 3, and we characterized it with the aid of X-ray crystallography. Transformation of complexes 1 and 2 to intermediate complex 3 and finally to 4 has been established by UV-vis spectroscopy, fluorescence spectroscopy, ESI-MS spectroscopy, 1H NMR spectroscopy, and X-ray crystallography. The spontaneity of the above conversion is well supported by thermodynamic aspects as reflected from density functional theoretical calculations.

Guest-Responsive Reversible Electron Transfer in a Crystalline Porous Framework Supported by a Dynamic Building Node.

We demonstrate a redox-active, crystalline donor-acceptor (D-A) assembly in which the electron transfer (ET) process can be reversibly switched. This ET process, induced by a guest-responsive structural transformation at room temperature, is realized in a porous, metal-organic framework (MOF), having anthracene (D)-naphthalenediimide (A) as struts. A control MOF structure obtained by a solvent-assisted linker exchange (SALE) method, replacing an acceptor strut with a neutral one, supported the switchable electronic states in the D-A MOF. Combined investigations with X-ray diffraction, spectroscopy, and theoretical analyses revealed the dynamic metal paddle-wheel node as a critical unit for controlling structural flexibility and the corresponding unprecedented ET process.

Dynamic Resolution of Piezosensitivity in Single Crystals of π-Conjugated Molecules.

Targeted synthesis of piezoresponsive small molecules and in-depth understanding of their mechanism is of utmost importance for the development of smart devices. This work reports the synthesis, structure and piezosensitivity of a bola-amphiphile 1,4-bis(pentyloxy)-2,5-bis(2-pyridineethynyl)-benzene (C5-PPB). Depending on the rate of compression, two different phases in C5-PPB can be generated. The ambient-pressure α-phase is stable up to 0.8 GPa, beyond which it undergoes an isostructural transformation to ß-phase, accompanied by a clearly visible elongation of the crystal. This α-to-ß phase transition requires the sample to be compressed slowly. When quickly compressed, phase α persists to about 1.5 GPa, beyond which its amorphization starts, accompanied by the appearance of irregular grooves on the largest faces. Mechanical pressure also affects the optical property of C5-PPB, which shows reversible mechanochromism with a green to cyan transformation in the emission, associated with a 15 nm shift in the maxima. The conductivity of C5-PPB as a direct outcome of its crystal packing has also been studied.

Photoswitchable J-Aggregated Processable Organogel by Integrating a Photochromic Acceptor.

A novel π-chromophoric 1,4-bis(anthracenylethynyl)benzene (BAB)-based highly emissive J-aggregated organogel has been synthesized and characterized. Single-crystal structure determination of asymmetric π-chromophoric bola-amphiphilic BAB1 (dodecyl and triethyleneglycolmonomethylether containing side chains of bis(anthracenylethynyl)benzene) supports J-aggregation. Further, a photochromic acceptor chromophore, 4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-2-carbaldehyde), is noncovalently encapsulated in the gel and photoswitching studies have been performed based on photochromic Förster resonance energy transfer. The modulated emission of the processable soft material is further exploited for rewritable display. However, BAB2 (dodecyl side chain on both sides) does not show gelation property due to its low solubility.

Solvent Adaptive Dynamic Metal-Organic Soft Hybrid for Imaging and Biological Delivery.

A solvent responsive dynamic nanoscale metal-organic framework (NMOF) [Zn(1 a)(H2 O)2 ] has been devised based on the self-assembly of ZnII and asymmetric bola-amphiphilic oligo-(p-phenyleneethynylene) (OPE) dicarboxylate linker 1 a having dodecyl and triethyleneglycolmonomethylether (TEG, polar) side chains. In THF solvent, NMOF showed nanovesicular morphology (NMOF-1) with surface decorated dodecyl chains. In water and methanol, NMOF exhibited inverse-nanovesicle (NMOF-2) and nanoscroll (NMOF-3) morphology, respectively, with surface projected TEG chains. The pre-formed NMOFs also unveiled reversible solvent responsive transformation of different morphologies. The flexible NMOF showed cyan emission and no cytotoxicity, allowing live cell imaging. Cisplatin (14.4 wt %) and doxorubicin (4.1 wt %) were encapsulated in NMOF-1 by non-covalent interactions and, in vitro and in vivo drug release was studied. The drug loaded NMOFs exhibited micromolar cytotoxicity.

Selective detection of DABCO using a supramolecular interconversion as fluorescence reporter.

The quantitative double self-sorting between the three-component rectangle [Cu4(1)2(2)2]4+ and the four-component sandwich complex [Cu2(1)(2)(4)]2+ is triggered by inclusion and release of DABCO (4). The fully reversible and clean switching between two multicomponent supramolecular architectures can be monitored by fluorescence changes at the zinc porphyrin sites. The structural changes are accompanied by a huge spatial contraction/expansion of the zinc porphyrin-zinc porphyrin distances that change from 31.2/38.8 Å to 6.6 Å and back. The supramolecular interconversion was used for the highly selective detection of DABCO in a mixture of other similar compounds.

Excitation Energy Transfer Supported Amplified Charge-Transfer Emission in an Anthracenedicarboxylate- and Bipyridophenazine-Based Coordination Complex.

A highly luminescent tetrameric zinc(II) complex, {[Zn4(adc)3(bpz)6(HCOO)2]·2H2O} (1; adc = 9,10-anthracenedicarboxylate and bpz = bipyridophenazine), was synthesized by a solvothermal technique and characterized by single-crystal X-ray diffraction. The linear tetrameric units extend into three dimensions via π stacking of adc/bpz and bpz/bpz and multiple CH-π interactions. The compound shows strong red emission at 597 nm (λex = 480 nm), which is attributed to charge-transfer (CT) emission within an adc/bpz donor-acceptor pair. This is also supported by density functional theory computations. Interestingly, the CT emission is amplified by energy transfer from another adc linker that is not involved in the CT interaction.

Post-Synthetic Decoupling of On-Surface-Synthesized Covalent Nanostructures from Ag(111).

The on-surface synthesis of covalent organic nanosheets driven by reactive metal surfaces leads to strongly adsorbed organic nanostructures, which conceals their intrinsic properties. Hence, reducing the electronic coupling between the organic networks and commonly used metal surfaces is an important step towards characterization of the true material. We demonstrate that post-synthetic exposure to iodine vapor leads to the intercalation of an iodine monolayer between covalent polyphenylene networks and Ag(111) surfaces. The experimentally observed changes from surface-bound to detached nanosheets are reproduced by DFT simulations. These findings suggest that the intercalation of iodine provides a material that shows geometric and electronic properties substantially closer to those of the freestanding network.

Solving the puzzling competition of the thermal C(2)-C(6) vs Myers-Saito cyclization of enyne-carbodiimides.

The mechanism of the thermal cyclization of enyne-carbodiimides 7a-c has been studied computationally by applying the DFT method. The results indicate that enyne-carbodiimides preferentially follow the C(2)-C(6) (Schmittel) cyclization pathway in a concerted fashion although the Myers-Saito diradical formation is kinetically preferred. The experimentally verified preference of the C(2)-C(6) over the Myers-Saito pathway is guided by the inability of the Myers-Saito diradical to kinetically compete in the rate-determining trapping reactions, either inter- or intramolecular, with the concerted C(2)-C(6) cyclization. As demonstrated with enyne-carbodiimide 11, the Myers-Saito channel can be made the preferred pathway if the trapping reaction by hydrogen transfer is no more rate determining.

Nonstatistical dynamics in the thermal C2-C6/diels-alder cyclization of enyne-allenes: effect of topology.

The thermal C(2)-C(6) (Schmittel) cyclization of an enyne-allene with two aryl rings at the allene terminus experimentally leads to three formal Diels-Alder (DA) cycloaddition products, two of which (involving the dimethylamino phenyl unit) are shown to form in a nonstatistical process. DFT computations on the reaction paths reveal that the two aryl rings (Ph vs PhNMe2) do not interact in a dynamic manner as their minimum energy pathways (MEPs) are separated by a large barrier. The preferential formation of the more-hindered DA product 8 (ortho to the dimethylamino group) over the less-hindered product 9 (para to the dimethylamino group), despite the higher energy TS for 8, suggests the occurrence of nonstatistical dynamics in the cyclization onto the dimethylamino phenyl unit, though. Potential energy surface (PES) computations indicate that the large amount of nonstatistical dynamics (97%) arises from facile IRC dynamics (left picture) that is compared with the non-IRC dynamics of a related system (∼76%, right picture, J. Org. Chem. 2014, 79, 2368).

Quantification of nonstatistical dynamics in an intramolecular Diels-Alder cyclization without trajectory computation.

Experimental and computational (DFT) investigations reveal that enyne-allenes with an aryl group as probe at the allene terminus follow a dynamic non-IRC Diels-Alder cyclization pathway. Starting from two separate C(2)-C(6) (Schmittel) transition states (TS), two distinct reaction paths originate that share a common diradical intermediate, however, without mixing! Because the momentum of the initial TS is transmitted into product formation, we suggest a simple protocol without trajectory computations to estimate the fraction of molecules that follow nonstatistical dynamics: It was calculated from the partitioning at the TSs, as derived from DFT computations, and the experimental ratio. The thus-determined percentage of dynamically reacting molecules only slightly depends on the depth of the intermediate well but rather on ΔΔG(‡) of the initial and the follow-up transition states.

Nonstatistical dynamics in the thermal Garratt-Braverman/[1,5]-H shift of one ene-diallene: an experimental and computational study.

A mechanistic study of the thermal Garratt-Braverman/[1,5]-H shift of ene-diallene 6 leading to alkenes (E)-8 and (Z)-8 is reported. The product ratio was found to be temperature-independent and does not agree with the computed energy barriers (i.e., TS2E(⧧) and TS2Z(⧧)). On the basis of experimental and DFT computational results, we propose a mechanism that is strongly controlled by nonstatistical dynamic effects.

A one-pot multistep cyclization yielding thiadiazoloimidazole derivatives.

A versatile synthetic procedure is described to prepare the benzimidazole-fused 1,2,4-thiadiazoles 2a-c via a methanesulfonyl chloride initiated multistep cyclization involving the intramolecular reaction of an in-situ generated carbodiimide with a thiourea unit. The structure of the intricate heterocycle 2a was confirmed by single-crystal X-ray analysis and its mechanism of formation supported by DFT computations.

Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes.

The Diels-Alder (DA) reaction channel of the thermal C(2)-C(6) (Schmittel) cyclization of enyne-allenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C(2)-C(6)/DA cyclization steering it either to a stepwise or a concerted course. Temperature independent product ratios, selectivity of product formation, and computational results obtained at (U)BLYP/6-31G(d) level unveil a mechanism that is strongly controlled by nonstatistical dynamics.

Heteroleptic metallosupramolecular racks, rectangles, and trigonal prisms: stoichiometry-controlled reversible interconversion.

A simple approach toward preparation of heteroleptic two-dimensional (2D) rectangles and three-dimensional (3D) triangular prisms is described utilizing the HETPYP (HETeroleptic PYridyl and Phenanthroline metal complexes) concept. By mixing metal-loaded linear bisphenanthrolines of varying lengths with diverse (multi)pyridine (py) ligands in a proper ratio, six different self-assembled architectures arise cleanly and spontaneously in the absence of any template. They are characterized by (1)H and DOSY NMR, ESI-FT-ICR mass spectrometry as well as by Job plots and UV-vis titrations. Density functional theory (DFT) computations provide information about each structure. A stoichiometry-controlled supramolecule-to-supramolecule interconversion based on the relative amounts of metal bisphenanthroline and bipyridine forces the rectangular assembly to reorganize to a rack architecture and back to the rectangle, as clearly supported by variable temperature and DOSY NMR as well as dynamic light scattering data. The highly dynamic nature of the assemblies represents a promising starting point for constitutional dynamic materials.

Biomimetic Approach toward Visible Light-Driven Hydrogen Generation Based on a Porphyrin-Based Coordination Polymer Gel.

There has been a widespread interest in developing self-assembled porphyrin nanostructures to mimic nature's light-harvesting processes. Herein, porphyrin-based coordination polymer gel (CPG) has been developed as a "soft" photocatalyst material for hydrogen (H2) production from water under visible light. The CPG offers a hierarchical nanofibrous network structure obtained through self-assembly of a terpyridine alkyl-amide appended porphyrin (TPY-POR)-based low molecular weight gelator with ruthenium ions (RuII) and produces H2 with a rate of 5.7 mmol g-1 h-1 in the presence of triethylamine (TEA) as a sacrificial electron donor. Further, the [Fe2(bdt)(CO)6] (dbt = 1,2-benzenedithiol) cocatalyst, which can mimic the activity of iron hydrogenase, is coassembled in the CPG and shows remarkable improvement in H2 evolution (catalytic activity; rate ∼10.6 mmol g-1 h-1 and turnover number ∼1287). The significant enhancement in catalytic activity was supported by several controlled experiments, including femtosecond transient absorption (TA) spectroscopy and also DFT calculation. The TA study supported the cascade electron transfer process from porphyrin core to [Ru(TPY)2]2+ center, and subsequently, the electron transfers to the cocatalyst [Fe2(bdt)(CO)6] for H2 production.

Smart high-yield tomato cultivation: precision irrigation system using the Internet of Things.

The Internet of Things (IOT)-based smart farming promises ultrafast speeds and near real-time response. Precision farming enabled by the Internet of Things has the potential to boost efficiency and output while reducing water use. Therefore, IoT devices can aid farmers in keeping track crop health and development while also automating a variety of tasks (such as moisture level prediction, irrigation system, crop development, and nutrient levels). The IoT-based autonomous irrigation technique makes exact use of farmers' time, money, and power. High crop yields can be achieved through consistent monitoring and sensing of crops utilizing a variety of IoT sensors to inform farmers of optimal harvest times. In this paper, a smart framework for growing tomatoes is developed, with influence from IoT devices or modules. With the help of IoT modules, we can forecast soil moisture levels and fine-tune the watering schedule. To further aid farmers, a smartphone app is currently in development that will provide them with crucial data on the health of their tomato crops. Large-scale experiments validate the proposed model's ability to intelligently monitor the irrigation system, which contributes to higher tomato yields.