Dioxygenase Chemistry in Nucleophilic Aldehyde Deformylations Utilizing Dicopper O2-Derived Peroxide Complexes.

The chemistry of copper-dioxygen complexes is relevant to copper enzymes in biology as well as in (ligand)Cu-O2 (or Cu2-O2) species utilized in oxidative transformations. For overall energy considerations, as applicable in chemical synthesis, it is beneficial to have an appropriate atom economy; both O-atoms of O2(g) are transferred to the product(s). However, examples of such dioxygenase-type chemistry are extremely rare or not well documented. Herein, we report on nucleophilic oxidative aldehyde deformylation reactivity by the peroxo-dicopper(II) species [Cu2II(BPMPO-)(O22-)]1+ {BPMPO-H = 2,6-bis{[(bis(2-pyridylmethyl)amino]methyl}-4-methylphenol)} and [Cu2II(XYLO-)(O22-)]1+ (XYLO- = a BPMPO- analogue possessing bis(2-{2-pyridyl}ethyl)amine chelating arms). Their dicopper(I) precursors are dioxygenase catalysts. The O2(g)-derived peroxo-dicopper(II) intermediates react rapidly with aldehydes like 2-phenylpropionaldehyde (2-PPA) and cyclohexanecarboxaldehyde (CCA) in 2-methyltetrahydrofuran at -90 °C. Warming to room temperature (RT) followed by workup results in good yields of formate (HC(O)O-) along with ketones (acetophenone or cyclohexanone). Mechanistic investigation shows that [Cu2II(BPMPO-)(O22-)]1+ species initially reacts reversibly with the aldehydes to form detectable dicopper(II) peroxyhemiacetal intermediates, for which optical titrations provide the Keq (at -90 °C) of 73.6 × 102 M-1 (2-PPA) and 10.4 × 102 M-1 (CCA). In the reaction of [Cu2II(XYLO-)(O22-)]1+ with 2-PPA, product complexes characterized by single-crystal X-ray crystallography are the anticipated dicopper(I) complex, [Cu2I(XYLO-)]1+ plus a mixed-valent Cu(I)Cu(II)-formate species. Formate was further identified and confirmed by 1H NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS) analysis. Using 18O2(g)-isotope labeling the reaction produced a high yield of 18-O incorporated acetophenone as well as formate. The overall results signify that true dioxygenase reactions have occurred, supported by a thorough mechanistic investigation.

Intramolecular Phenolic H-Atom Abstraction by a N3ArOH Ligand-Supported (µ-η2:η2-Peroxo)dicopper(II) Species Relevant to the Active Site Function of oxy-Tyrosinase.

Synthetic side-on peroxide-bound dicopper(II) (SP) complexes are important for understanding the active site structure/function of many copper-containing enzymes. This work highlights the formation of new {CuII(µ-η2:η2-O22-)CuII} complexes (with electronic absorption and resonance Raman (rR) spectroscopic characterization) using tripodal N3ArOH ligands at -135 °C, which spontaneously participate in intramolecular phenolic H-atom abstraction (HAA). This results in the generation of bis(phenoxyl radical)bis(µ-OH)dicopper(II) intermediates, substantiated by their EPR/UV-vis/rR spectroscopic signatures and crystal structural determination of a diphenoquinone dicopper(I) complex derived from ligand para-C═C coupling. The newly observed chemistry in these ligand-Cu systems is discussed with respect to (a) our Cu-MeAN (tridentate N,N,N',N',N″-pentamethyldipropylenetriamine)-derived model SP species, which was unreactive toward exogenous monophenol addition (J. Am. Chem. Soc. 2012, 134, 8513-8524), emphasizing the impact of intramolecularly tethered ArOH groups, and (b) recent advances in understanding the mechanism of action of the tyrosinase (Ty) enzyme.

Coordination Variations within Binuclear Copper Dioxygen-Derived (Hydro)Peroxo and Superoxo Species; Influences upon Thermodynamic and Electronic Properties.

Copper ion is a versatile and ubiquitous facilitator of redox chemical and biochemical processes. These include the binding of molecular oxygen to copper(I) complexes where it undergoes stepwise reduction-protonation. A detailed understanding of thermodynamic relationships between such reduced/protonated states is key to elucidate the fundamentals of the chemical/biochemical processes involved. The dicopper(I) complex [CuI2(BPMPO-)]1+ {BPMPOH = 2,6-bis{[(bis(2-pyridylmethyl)amino]methyl}-4-methylphenol)} undergoes cryogenic dioxygen addition; further manipulations in 2-methyltetrahydrofuran generate dicopper(II) peroxo [CuII2(BPMPO-)(O22-)]1+, hydroperoxo [CuII2(BPMPO-)(-OOH)]2+, and superoxo [CuII2(BPMPO-)(O2•-)]2+ species, characterized by UV-vis, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies, and cold spray ionization mass spectrometry. An unexpected EPR spectrum for [CuII2(BPMPO-)(O2•-)]2+ is explained by the analysis of its exchange-coupled three-spin frustrated system and DFT calculations. A redox equilibrium, [CuII2(BPMPO-)(O22-)]1+ ⇄ [CuII2(BPMPO-)(O2•-)]2+, is established utilizing Me8Fc+/Cr(η6-C6H6)2, allowing for [CuII2(BPMPO-)(O2•-)]2+/[CuII2(BPMPO-)(O22-)]1+ reduction potential calculation, E°' = -0.44 ± 0.01 V vs Fc+/0, also confirmed by cryoelectrochemical measurements (E°' = -0.40 ± 0.01 V). 2,6-Lutidinium triflate addition to [CuII2(BPMPO-)(O22-)]1+ produces [CuII2(BPMPO-)(-OOH)]2+; using a phosphazene base, an acid-base equilibrium was achieved, pKa = 22.3 ± 0.7 for [CuII2(BPMPO-)(-OOH)]2+. The BDFEOO-H = 80.3 ± 1.2 kcal/mol, as calculated for [CuII2(BPMPO-)(-OOH)]2+; this is further substantiated by H atom abstraction from O-H substrates by [CuII2(BPMPO-)(O2•-)]2+ forming [CuII2(BPMPO-)(-OOH)]2+. In comparison to known analogues, the thermodynamic and spectroscopic properties of [CuII2(BPMPO-)] O2-derived adducts can be accounted for based on chelate ring size variations built into the BPMPO- framework and the resulting enhanced CuII-ion Lewis acidity.

Transcriptional networks revealed late embryogenesis abundant genes regulating drought mitigation in aromatic Keteki Joha rice.

Climate change has become increasingly intertwined with the occurrence and severity of droughts. As global temperatures rise due to greenhouse gas emissions, weather patterns are altered, leading to shifts in precipitation levels and distribution. These exacerbate the risk of drought in many regions, with potentially devastating consequences. A comprehensive transcriptome analysis was performed on Keteki Joha, an aromatic rice from North East India, with the aim of elucidating molecular responses to drought. Numerous genes linked to drought were activated, with both ABA-dependent and ABA-independent pathways playing crucial roles. Upregulated genes were enriched with gene ontology terms with response to abscisic acid and abscisic acid-activated signalling pathway, suggesting the existence of an ABA-dependent pathway for drought mitigation. The upregulated genes were also enriched with responses to stress, water, heat, jasmonic acid, and hydrogen peroxide, indicating the presence of an ABA-independent pathway alongside the ABA-dependent mechanism. Weighted Correlation Network Analysis (WGCNA) identified 267 genes that specifically govern drought mitigation in Keteki Joha. The late embryogenesis abundant (LEA) gene family emerges as the most overrepresented in both RNA sequencing data and WGCNA analysis, suggesting their dominant role in mitigating drought. Notably, 31 LEA genes were induced in seedlings and 32 in mature stages under drought stress. The LEA3-1, LEA14/WSI18, RAB16A, RAB16B, DHN1, DHN6, LEA1, LEA3, LEA17, and LEA33 exhibited and established co-expression with numerous other drought stress-related genes, indicating their inseparable role in alleviating drought. Consequently, LEA genes have been proposed to be primary and crucial responders to drought in Keteki Joha.

Sequential Oxygenation of Bis(ß-diketiminate) on a Selective Diruthenium Platform.

This article demonstrated the redox-noninnocent phenylene-linked bis(ß-diketiminate) (L2-)-bridged first example of isomeric diruthenium(III)-acac species (acac = acetylacetonate) and its ability to activate dioxygen. The coordination of deprotonated L2- to the {Ru(acac)2} in bis(bidentate) mode led to isomeric {(acac)2RuIII}2(µ-L2-) (S = 1, 1-trans/1-cis, green). 1 displayed Ru(III)-based anisotropic EPR in CH3CN but without the resolution of the forbidden (ΔMs = 2) g1/2 signal at 77 K. 1-cis, however, slowly transformed to the energetically favored 1-trans form. 1 underwent two-step oxygenation at the Cß sites of L2- to form the ß-diketiminate/α-ketodiimine (L'-)-bridged mixed valent (acac)2RuIII(µ-L'-)RuII(acac)2 (2, S = 1/2, pink) followed by bis(α-ketodiimine) (L″)-bridged isovalent (acac)2RuII(µ-L″)RuII(acac)2 (3, S = 0, red). The role of O2 toward 1 → 2/3 was corroborated by 18O2 labeling experiment. Redox steps of 1-3 varied as a function of isomeric identity, bridge, and metal oxidation state. The calculated MOs and Mulliken spin densities attributed to the noninnocence of L2-, L'-, and L″ in the respective complexes. Spectrophotometric monitoring of 1 → 2 revealed pseudo-first-order rate constants (105k s-1) of 1.8 (303 K), 3.5 (313 K), 7.7 (323 K), and 17.0 (333 K) and ΔH⧧/ΔS⧧/ΔG⧧ of 14.3 kcal mol-1/-33.1 cal mol-1 K-1/24.2 kcal mol-1 (298 K), respectively. Moreover, characterization of the short-lived blue intermediate obtained during the conversion of 1 → 2/3 upon exposure to O2 supported its valence tautomeric form (VT1, RuIII-L2--RuIII ↔ RuIII-L•--RuII, S = 1), which in effect facilitated oxygen activation at the ligand backbone.

Genome-wide identification and expression analysis of the Pisum sativum (L.) APETALA2/ethylene-responsive factor (AP2/ERF) gene family reveals functions in drought and cold stresses.

AP2/ERF (APETALA2/Ethylene Response Factor) is a family of transcription factors that play essential roles in regulating gene expression in response to various environmental stimuli, including biotic and abiotic stresses, hormone signaling, and developmental processes. Pisum sativum (L.), commonly known as garden pea, is a winter crop sensitive to high temperatures and can also be affected by extreme cold and drought conditions. This study performed a genome-wide analysis of AP2/ERF genes and identified 153 AP2/ERF genes in P. sativum. Based on the conserved AP2/ERF domain and sequence homology, they were classified into AP2 (APETALA2), ERF (Ethylene Response Factor), DREB (Dehydration responsive element-binding), RAV (Related to Abscisic Acid Insensitive 3/ Viviparous 1) and Soloist subfamily. The DREB and ERF subfamily were further divided into groups A1-6 and B1-B6. Tandem and segmental duplication events were more frequent in the ERF subfamily, which can have important implications for their evolution and functional diversification. Under cold stress, the expression of DREB1A was highly induced in leaves, whereas DREB1B was suppressed. Similarly, the DREB2A, DREB2C, DREB2E, and DREB2F were induced in leaves under drought stress. The putative target genes of AP2/ERF transcription factors are highly diversified, suggesting that they play essential roles in various physiological responses in plants, including responses to biotic and abiotic stresses as well as developmental processes. Thus, this study of AP2/ERF genes and their functions provides valuable insight into how P. sativum responds to different environmental conditions, including cold and drought stresses.

Unique Metal-Ligand Interplay in Directing Discrete and Polymeric Derivatives of Isomeric Azole-Carboxylate. Varying Electronic Form, C-C Coupling, and Receptor Feature.

This article dealt with the ruthenium and osmium derivatives of isomeric 1H-indazole-3-carboxylic acid/2H-indazole-3-carboxylic acid (H2L1) and 1H-benzimidazole-2-carboxylic acid (H2L2) along with the π-acidic bpy (bpy = 2,2'-bipyridine) and pap (pap = 2-phenylazopyridine) co-ligands. It thus extended structurally authenticated monomeric ([(bpy)2RuII(HL1-)]ClO4 [1]ClO4, (pap)2RuII(L12-) 2, (bpy)2OsII(L12-) 3, (pap)2OsII(L12-) 4, (bpy)2RuII(L22-) 5, (bpy)2OsII(L22-) 8, and (pap)2OsII(L22-) 9) and dimeric ([(bpy)2RuII(µ-L22-)RuII(bpy)2](ClO4)2 [6](ClO4)2) complexes. It also described modified L2'2- (L2'2- = 2,2'-bisbenzimidazolate)-bridged [(pap)2RuII(µ-L2'2-)RuII(pap)2](ClO4)2 [7](ClO4)2, where L2'2- was developed selectively with the {Ru(pap)2} metal fragment via in situ intermolecular C-C coupling of the two units of decarboxylated benzimidazolate. Moreover, chemical oxidation (OsII to OsIII) of (bpy)2OsII(L12-) 3 (E0 = 0.11 V versus SCE) and (bpy)2OsII(L22-) 8 (E0 = 0.12 V versus SCE) by AgClO4 yielded unprecedented OsIII-AgI derived polymeric {[(bpy)2OsIII-L12--AgI(CH3CN)](ClO4)2}n {[10](ClO4)2}n and dimeric [(bpy)2OsIII-L22--AgI(CH3CN)](ClO4)2 [11](ClO4)2 complexes as a function of trans and cis orientations of the active N2 donor with special reference to the carboxylate O2 of L2-, respectively. Microscopic (FE-SEM, TEM-EDX, and AFM) and DLS experiments suggested a homogeneously dispersed hollow spherical shaped morphology of {[10](ClO4)2}n with an average particle size of 200-400 nm as well as its non-dissociative feature in the aprotic medium. Experimental (structure, spectroscopy, and electrochemistry) and theoretical (DFT/TD-DFT) explorations revealed a redox non-innocent feature of L2- in the present coordination situations and the selective anion sensing (X = F-, CN-, and OAc-) event of [1]ClO4 involving a free NH group at the backface of HL1-, which proceeded via the NH···X hydrogen bonding interaction.

Photoinduced Regioselective Olefination of Arenes at Proximal and Distal Sites.

The Fujiwara-Moritani reaction has had a profound contribution in the emergence of contemporary C-H activation protocols. Despite the applicability of the traditional approach in different fields, the associated reactivity and regioselectivity issues had rendered it redundant. The revival of this exemplary reaction requires the development of a mechanistic paradigm that would have simultaneous control on both the reactivity and regioselectivity. Often, the high thermal energy required to promote olefination leads to multiple site functionalizations. To this aim, we established a photoredox catalytic system constituting a merger of palladium/organo-photocatalyst (PC) that forges oxidative olefination in an explicit regioselective fashion with diverse arenes and heteroarenes. Visible light plays a significant role in executing "regioresolved" Fujiwara-Moritani reactions without the requirement of silver salts and thermal energy. The catalytic system is also amenable toward proximal and distal olefination aided by the respective directing groups (DGs), which entails the versatility of the protocol in engaging the entire spectrum of C(sp2)-H olefination. Furthermore, streamlining the synthesis of natural products, chiral molecules, drugs, and diversification through late-stage functionalizations underscore the importance of this sustainable protocol. The photoinduced attainment of this regioselective transformation is mechanistically established through control reactions and kinetic studies.

Dioxygen Activation by Redox-Active Bis(aldimine) Ligand Bridged Diruthenium Complex Possessing Singlet Ground State.

The unexplored 'actor' behavior of redox-active bis(aldimine) congener, p-phenylene-bis(picoline)aldimine (L1), towards dioxygen activation and subsequent functionalization of its backbone was demonstrated on coordination with {Ru(acac)2 } (acac= acetylacetonate). Reaction under aerobic condition led to the one-pot generation of dinuclear complexes with unperturbed L1, imino-carboxamido (L2- ), and bis(carboxamido) (L32- )-bridged isovalent {RuII (µ-L1)RuII }, 1/ {RuIII (µ-L32- )RuIII }, 3 and mixed-valent {RuII (µ-L2- )RuIII }, 2. Authentication of the complexes along with the redox non-innocence behavior of their bridge have been validated through structure, spectroelectrochemistry and DFT calculations. Kinetic and isotope labelling experiments together with DFT analyzed transition states justified the consideration of redox shuttling at metal/L1 interface for 3 O2 activation despite of the closed shell configuration of 1 (S=0) to give carboxamido derived 2/3.

Redox-Induced Intramolecular C-C Coupling of Acyclic Bis(2-pyridylmethylene)ethylenediamine on a Ru(acac)2 Platform.

The paper documents redox-triggered C-C coupling of acyclic N,N'-bis(2-pyridylmethylene)ethylenediamine (BPE) to yield 2,3-bis(2-pyridyl)pyrazine (DPP) upon coordination to an electron-rich {Ru(acac)2} (acac = acetylacetonate) unit. This led to DPP-bridged [{Ru(acac)2}2(DPP)]0/+ (2 and [2]ClO4) along with the unperturbed BPE-bridged [{Ru(acac)2}2(BPE)] (1). On the contrary, electron-poor {Ru(Cl)(H)(CO)(PPh3)3} yielded BPE-bridged [3](ClO4)2 as an exclusive product. Synergistic metal (Ru)-ligand (BPE) redox participation toward chemical noninnocence of the Schiff base ligand and DPP-mediated electronic communication in RuIIRuIII-derived [2]ClO4 are addressed.

On the Question of S-S Bond Cleavage of 2,2'-Dithiodipyridine on Selective Ru and Os Platforms. MLCT or Hydride or Solvent Mediated Event.

This article deals with the S-S bond scission of the model substrate 2,2'-dithiodipyridine (DTDP) in the presence of a selective set of metal precursors: RuII(acac)2, [RuIICl2(PPh3)3], [RuIIHCl(CO)(PPh3)3], [RuII(H)2(CO)(PPh3)3], [RuII(bpy)2Cl2], [RuII(pap)2Cl2], [OsII(bpy)2Cl2], and [OsII(pap)2Cl2] (acac, acetylacetonate; bpy, 2,2'-bipyridine; pap, 2-phenylazopyridine). This led to the eventual formation of the corresponding mononuclear complexes containing the cleaved pyridine-2-thiolate unit in 1-4/[5]ClO4-[8]ClO4. The formation of the complexes was ascertained by their single-crystal X-ray structures, which also established sterically constrained four-membered chelate (average N1-M-S1 angle of 67.89°) originated from the in situ-generated pyridine-2-thiolate unit. Ruthenium(III)-derived one-electron paramagnetic complexes 1-2 (S = 1/2, magnetic moment/B.M. = 1.82 (1)/1.81(2)) exhibited metal-based anisotropic electron paramagnetic resonance (EPR) (Δg: 1/2 = 0.64/0.93, ⟨g⟩: 1/2 = 2.173/2.189) and a broad 1H nuclear magnetic resonance (NMR) signature due to the contact shift effect. The spectroelectrochemical and electronic structural aspects of the complexes were analyzed experimentally in combination with theoretical calculations of density functional theory (DFT and TD-DFT). The unperturbed feature of DTDP even in refluxing ethanol over a period of 10 h can be attributed to the active participation of the metal fragments in facilitating S-S bond cleavage in 1-4/[5]ClO4-[8]ClO4. It also revealed the following three probable pathways toward S-S bond cleavage of DTDP as a function of metal precursors: (i) the metal-to-ligand charge-transfer (MLCT) (RuII → σ* of DTDP)-driven metal oxidation (RuII → RuIII) process in the case of relatively electron-rich metal fragments {RuII(acac)2} or RuIICl2 in 1 or 2, respectively; (ii) metal hydride-assisted formation of 3 or 4 with the concomitant generation of H2; and (iii) S-S bond reduction with the simultaneous oxidation of the solvent benzyl alcohol to benzaldehyde.

Substrate-Rhodium Cooperativity in Photoinduced ortho-Alkynylation of Arenes.

In the realm of metallaphotocatalytic C-H activation strategy, the direct excitation of the transition metal which plays the dual role of light energy harnessing alongside performing the bond breaking and forming is a rare phenomenon. In this context we have developed the first photo-induced Rh-catalyzed ortho-alkynylation under ambient conditions without the requirement of silver salt, photocatalyst (PC) or any engineered substrate or catalyst. The transformation functions by the specific cooperative effect of a six-membered rhodacycle which is the photo-responsive species. The catalytic system allows the conjugation of arenes with sp3 -rich pharmacophoric fragments. The control experiments as well as the computational studies resolve the mechanistic intricacies for this transformation. An outer sphere electron transfer process from Rh to alkynyl radical is operative for the present photo-induced transformation over the more common oxidative addition or 1,2-migratory insertion pathways.

Comparative Transcriptomics of Lowland Rice Varieties Uncovers Novel Candidate Genes for Adaptive Iron Excess Tolerance.

Iron (Fe) toxicity is a major challenge for plant cultivation in acidic waterlogged soil environments, where lowland rice is a major staple food crop. Only few studies have addressed the molecular characterization of excess Fe tolerance in rice, and these highlight different mechanisms for Fe tolerance. Out of 16 lowland rice varieties, we identified a pair of contrasting lines, Fe-tolerant Lachit and -susceptible Hacha. The two lines differed in their physiological and morphological responses to excess Fe, including leaf growth, leaf rolling, reactive oxygen species generation and Fe and metal contents. These responses were likely due to genetic origin as they were mirrored by differential gene expression patterns, obtained through RNA sequencing, and corresponding gene ontology term enrichment in tolerant vs. susceptible lines. Thirty-five genes of the metal homeostasis category, mainly root expressed, showed differential transcriptomic profiles suggestive of an induced tolerance mechanism. Twenty-two out of these 35 metal homeostasis genes were present in selection sweep genomic regions, in breeding signatures, and/or differentiated during rice domestication. These findings suggest that Fe excess tolerance is an important trait in the domestication of lowland rice, and the identified genes may further serve to design the targeted Fe tolerance breeding of rice crops.

Osmium(II)-Coordination Induced C-C Bond Functionalization of Bis-lawsone.

Metal-coordination-driven C-C bond functionalization without involvement of the traditional route of oxidative addition, insertion, and reductive elimination has gained immense importance. In this context, the present Communication highlights the facile ring contraction process of the deprotonated bis-lawsone (L2-) to functionalized L12- upon coordination to {Os(bpy)2} or isomeric {Os(pap)2} (bpy = 2,2'-bipyridine and pap = 2-phenylazopyridine) in 1-3. Further, recognition of fractional redox noninnocence of L1 in 1+-3+ via experimental and theoretical events facilitated its inclusion in the redox noninnocent family.

Radical versus Nonradical States of Azobis(benzothiazole) as a Function of Ancillary Ligands on Selective Ruthenium Platforms.

The paper deals with the electronic impact of ancillary ligands on the varying redox features of azobis(benzothiazole) (abbt) in the newly introduced mononuclear ruthenium complexes [Ru(pap)2(abbt)]n (1n) and [Ru(bpy)2(abbt)]n (2n), where pap = 2-phenylazopyridine and bpy = 2,2'-bipyridine. In this regard, the complexes [RuII(pap)2(abbt•-)]ClO4 ([1]ClO4), [RuII(pap)2(abbt0)](ClO4)2 ([1](ClO4)2), [RuII(bpy)2(abbt0)](ClO4)2 ([2](ClO4)2), and [RuII(bpy)2(abbt•-)]ClO4 ([2]ClO4) were structurally and spectroscopically characterized. Unambiguous assignments of the aforestated radical and nonradical forms of abbt in 1+/2+ and 12+/22+, respectively, were made primarily based on their redox-sensitive azo (N═N) bond distances as well as by their characteristic electron paramagnetic resonance (EPR)/NMR signatures. Although the radical form of abbt•- was isolated as an exclusive product in the case of strongly π-acidic pap-derived 1+, the corresponding moderately π-acidic bpy ancillary ligand primarily delivered an oxidized form of abbt0 in 22+, along with the radical form in 2+ as a minor (<10%) component. The oxidized abbt0-derived [1](ClO4)2 was, however, obtained via the chemical oxidation of [1]ClO4. Both 1+ and 22+ displayed multiple closed by reversible redox processes (one oxidation O1 and four successive reductions R1-R4) within the potential window of ±2.0 V versus saturated calomel electrode. The involvement of metal-, ligand-, or metal/ligand-based frontier molecular orbitals along the redox chain was assigned based on the combined experimental (structure, EPR, and spectroelectrochemisry) and theoretical [density functional theory (DFT): molecular orbitals, Mulliken spin densities/time-dependent DFT] investigations. It revealed primarily ligand (abbt/pap or bpy)-based redox activities, keeping the metal ion as a simple spectator. Moreover, frontier molecular orbital analysis corroborated the initial isolation of the radical and nonradical species for the pap-derived 1+ and bpy-derived 22+ as well as facile reduction of pap and abbt in 1+ and 2+, respectively.

The SlNAC2 transcription factor from tomato confers tolerance to drought stress in transgenic tobacco plants.

Drought is a key environmental factor that restricts crop growth and productivity. Plant responses to water-deficit stress at the whole plant level are mediated by stress-response gene expression through the action of transcription factors (TF). The NAC (NAM/ATAF/CUC) transcription factor family has been well documented in its role in improving plant abiotic stress tolerance. In the present study we evaluated the effects of overexpression of SlNAC2 TF on the photosynthetic machinery, relative water content (RWC), reactive oxygen species, antioxidants and proline levels in tobacco plants exposed to a water-deficit treatment. Shoot growth and seed formation were also evaluated before, during and following water-deficit to determine any morphological consequences of transgene expression. The transgenic plants maintained higher RWC and chlorophyll levels over 21 days after withholding water and stomatal conductance until the 16th day of water-deficit. Overexpression of SlNAC2 in tobacco increased proline levels, improved seed setting and delayed leaf senescence of the transgenic plants. Reactive oxygen species accumulated at lower levels in the dehydrated transgenic plants but no significant difference in superoxide dismutase and catalase content were seen between the genotypes. The conversion of glutathione to oxidized glutathione was significantly higher in the transgenic plants, supported by increased glutathione reductase transcript levels. Our results indicate that overexpression of SlNAC2 in tobacco improved survival during and recovery from water-deficit stress, without an associated biomass penalty under irrigation. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s12298-021-00996-2.

Metal-to-Ligand Charge Transfer Induced Valence Tautomeric Forms of Non-Innocent 2,2'-Azobis(benzothiazole) in Ruthenium Frameworks.

The impact of metal-to-ligand charge transfer towards the redox noninnocence of 2,2'-azobis(benzothiazole) (abbt) has been highlighted on coordination to {RuII (acac)2 } (acac=2,4-pentanedionato). It led to the authentication of a series of mononuclear and dinuclear complexes incorporating variable oxidation states of abbt (abbt0/.-/2- ). Mononuclear 1 was identified as [RuIII (abbt.- )], a MLCT excited state of [RuII (abbt)]. Dinuclear 2 was however recognized as two discrete redox isomers: (i) radical bridged mixed-valent meso-[Ru2.5 (µ-abbt.- )Ru2.5 ] (2a) and (ii) dianionic ligand bridged isovalent meso-[RuIII (µ-abbt2- )RuIII ] (2b), demonstrating unprecedented structural confirmation of valence tautomerism in azo-based ligand systems. A crystal structure of [2]ClO4 validated the formation of [RuIII (µ-abbt.- ) RuIII ]ClO4 . Analysis of electronic structural forms of 1 and 2 in accessible redox states via spectroelectrochemistry and DFT revealed their electron reservoir feature.

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation.

"Chemical noninnocence" of metal-coordinated 2-picolylamine (PA) derivatives has been introduced upon its reaction with the metal precursor [RuII(Cl)(H)(CO)(PPh3)3] under basic conditions. This in effect leads to the facile formation of metalated amide, imine, ring-cyclized pyrrole, and an N-dealkylated congener based on the fine-tuning of an amine nitrogen (Namine) and a methylene center (Cα) at the PA backbone. It develops oxygenated L1' in 1 and cyclized L4' in 4 upon switching of the Namine substituent of PA from aryl to an electrophilic pent-3-en-2-one moiety. On the other hand, imposing the substituent at the Cα position of PA modifies its reactivity profile, leading to a dehydrogenation (2/3) or N-dealkylation (6) process. The divergent reactivity profile of metalated PA is considered to proceed through a common dianionic intermediate. Further, a competitive scenario of C-H bond functionalization of coordinated PA versus the ligand-exchange process has been exemplified in the presence of external electrophile such as benzyl bromide or methylene iodide. Authentication of the product formation as well as elucidation of the reaction pathway has been addressed by their crystal structures and spectroscopic features in conjunction with the transition-state (TS) theory.

Discovery of genomic regions and candidate genes for grain weight employing next generation sequencing based QTL-seq approach in rice (Oryza sativa L.).

Rice (Oryza sativa L.) yield enhancement is one of the prime objectives of plant breeders. Elucidation of the inheritance of grain weight, a key yield component trait, is of paramount importance for raising the yield thresholds in rice. In the present investigation, we employed Next-Generation Sequencing based QTL-seq approach to identify major genomic regions associated with grain weight using mapping populations derived from a cross between BPT5204 and MTU3626. QTL-seq analysis identified three grain weight quantitative trait loci (QTL) viz., qGW1 (35-40 Mb), qGW7 (10-18 Mb), and qGW8 (2-5 Mb) on chromosomes 1, 7 and 8, respectively and all are found to be novel. Further, qGW8 was confirmed through conventional QTL mapping in F2, F3 and BC1F2 populations and found to explain the phenotypic variance of 17.88%, 16.70% and 15.00%, respectively, indicating a major QTL for grain weight. Based on previous reports, two candidate genes in the qGW8 QTL were predicted i.e., LOC_Os08g01490 (Cytochrome P450), and LOC_Os08g01680 (WD domain, G-beta repeat domain containing protein) and through in silico analysis they were found to be highly expressed in reproductive organs during different stages of grain development. Here, we have demonstrated that QTL-seq is one of the rapid approaches to uncover novel QTLs controlling complex traits. The candidate genes identified in the present study undoubtedly enhance our understanding of the mechanism and inheritance of the grain weight. These candidate genes can be exploited for yield enhancement after confirmation through complementary studies.

Plant-microbe Interactions for Sustainable Agriculture in the Post-genomic Era.

Plant-microbe interactions are both symbiotic and antagonistic, and the knowledge of both these interactions is equally important for the progress of agricultural practice and produce. This review gives an insight into the recent advances that have been made in the plant-microbe interaction study in the post-genomic era and the application of those for enhancing agricultural production. Adoption of next-generation sequencing (NGS) and marker assisted selection of resistant genes in plants, equipped with cloning and recombination techniques, has progressed the techniques for the development of resistant plant varieties by leaps and bounds. Genome-wide association studies (GWAS) of both plants and microbes have made the selection of desirable traits in plants and manipulation of the genomes of both plants and microbes effortless and less time-consuming. Stress tolerance in plants has been shown to be accentuated by association of certain microorganisms with the plant, the study and application of the same have helped develop stress-resistant varieties of crops. Beneficial microbes associated with plants are being extensively used for the development of microbial consortia that can be applied directly to the plants or the soil. Next-generation sequencing approaches have made it possible to identify the function of microbes associated in the plant microbiome that are both culturable and non-culturable, thus opening up new doors and possibilities for the use of these huge resources of microbes that can have a potential impact on agriculture.