Partial Reduction Research Articles

Synthesis of N-Alkyl-1,3-dihydro-2,1-benzisoxazoles.

We describe a practical method for the synthesis of various substituted N-alkyl-1,3-dihydro-2,1-benzisoxazoles and their 2,1-benzisoxazolone precursors starting from readily available methyl 2-nitrobenzoates. The method entails partial nitro reduction with hydrazine and rhodium on carbon to give the hydroxylamines, followed by base-mediated cyclization to give the corresponding benzisoxazol-3(1H)-ones. Subsequent alkylation is conducted under basic conditions and is followed by reduction to the target 1,3-dihydrobenzisoxazoles, achieved with lithium aluminum hydride in the presence of trimethylsilyl chloride.

Improvement of Biogas Productivity from Distillery Wastewater by Partial Potassium Reduction Pretreatment using Two-Step Microfiltration and Nanofiltration

The main purpose of the current study was to employ filtration pretreatment to lower the K concentration in distillery wastewater (DW) from a very high level (8800 mg/L) close to severe inhibition (>12000 mg/L) to 4350 mg/L, which was in the moderate toxic range (2500–4500 mg/L) for methanogens. The filtration pretreatment system consisted of the two steps of microfiltration (MF) to remove large solid particles and nanofiltration (NF) to reduce K concentration in the retained DW. Both steps of MF and NF were operated in batch mode with continuous recirculation. The permeate of the MF step was fed to the NF unit in conjunction with different dilution ratios (dilution water volume-to-feed volume) to lower the K content in the retentate. The higher the cumulative dilution ratio, the lower the K concentration in the retentate of the NF step. However, it has to be traded off against the increasing total volume of permeate with the higher cumulative dilution ratio. Thus, at the optimum cumulative dilution ratio of 0.5:1, the DW from filtration pretreatment with a high COD value of 111500 mg/L and a low K content of 4350 mg/L was found to have significantly higher methanogenic productivities in terms of average production rate and yields of both biogas and methane with a higher optimum COD loading rate, as compared to those of the untreated DW. Moreover, the use of the two-step filtration in this investigation could significantly lower the dilution ratio as compared to the sole dilution method (0.5:1 against 2:1).

A combined approach for comprehensive explanation of defects' thermodynamics in highly non-stoichiometric oxides: Case of RBaCo2O6-δ family (R = La, Nd, Pr, Sm, Gd, Eu, Ho and Y)

The thermodynamics of defect formation in layered perovskite-like cobaltites RBaCo2O6-δ (R = La, Nd, Pr, Sm, Gd, Eu, Ho and Y) was investigated via two distinct methods – (I) processing experimental data on oxygen non-stoichiometry using a quasichemical model and (II) employing a combined approach within the framework of density functional theory (DFT) under general gradient (GGA) and quasiharmonic Debye (QHDA) approximations. The outcomes of the first-principles calculations exhibit a plausible agreement with the fitting results, thereby confirming the validity of the developed model. The study reveals that key thermodynamic parameters governing defect formation, such as the enthalpy and entropy of oxygen exchange, as well as the enthalpy of oxygen disordering over nonequivalent crystallographic positions, exhibit correlations with the size of the rare-earth element R. In contrast, the enthalpy of charge disproportionation is demonstrated to be independent of the nature of the R atom. In Addition, it is suggested that when R = Eu, partial reduction of the latter may be observed in the lattice of EuBaCo2O6-δ. The findings indicate that, at a first approximation, the parameters of defect formation in RBaCo2O6-δ remain relatively independent on temperature and oxygen non-stoichiometry δ. The employed combined approach has been demonstrated to be reliable for assessing the thermodynamic functions of defect formation at elevated temperatures.

The Switching of the Type of a ROS Signal from Mitochondria: The Role of Respiratory Substrates and Permeability Transition

Flashes of superoxide anion (O2−) in mitochondria are generated spontaneously or during the opening of the permeability transition pore (mPTP) and a sudden change in the metabolic state of a cell. Under certain conditions, O2− can leave the mitochondrial matrix and perform signaling functions beyond mitochondria. In this work, we studied the kinetics of the release of O2− and H2O2 from isolated mitochondria upon mPTP opening and the modulation of the metabolic state of mitochondria by the substrates of respiration and oxidative phosphorylation. It was found that mPTP opening leads to suppression of H2O2 emission and activation of the O2− burst. When the induction of mPTP was blocked by its antagonists (cyclosporine A, ruthenium red, EGTA), the level of substrates of respiration and oxidative phosphorylation and the selective inhibitors of complexes I and V determined the type of reactive oxygen species (ROS) emitted by mitochondria. It was concluded that upon complete and partial reduction and complete oxidation of redox centers of the respiratory chain, mitochondria emit H2O2, O2−, and nothing, respectively. The results indicate that the mPTP- and substrate-dependent switching of the type of ROS leaving mitochondria may be the basis for O2−- and H2O2-selective redox signaling in a cell.

Modulation of persistent bladder pain in mice: The role of macrophage migration inhibitory factor, high mobility group box-1, and downstream signaling pathways.

Repeated intravesical activation of protease-activated receptor-4 (PAR4) serves as a model of persistent bladder hyperalgesia (BHA) in mice, which lasts several days after the final stimulus. Spinal macrophage migration inhibitory factor (MIF) and high mobility group box 1 (HMGB1) are critical mediators in the persistence of BHA. We aimed to identify effective systemic treatments for persistent BHA using antagonists or transgenic deletions. Persistent BHA was induced through transurethral instillations of a PAR4-activating peptide (PAR4-AP; 100 μM, 1 h; scrambled peptide, control) under anesthesia, administered on Days 0, 2, and 4. Lower abdominal hypersensitivity was measured on Days 0-4 and 7-9. Systemic injections from Days 2-8 included ISO-1 (a MIF antagonist), ethyl pyruvate (an inhibitor of HMGB1 release), phosphate-buffered saline, or 10% DMSO (vehicle control) in C57BL/6 mice. To examine the role of HMGB1 receptors, Toll-like receptor-4 (TLR4)-null mice or systemic treatment with FPS-ZM1 (receptor for advanced glycation end product [RAGE] antagonist) were used. In addition, TIR-domain-containing adaptor-inducing interferon-β (TRIF)-null mice were tested to assess the involvement of TLR4 signaling pathways. Micturition volume and frequency were assessed on Day 9, and the bladder was histopathologically examined to assess inflammation and edema. MIF antagonism significantly reversed persistent BHA, whereas HMGB1 antagonism led to a partial reduction of persistent BHA. TLR4 deficiency or systemic administration of FPS-ZM1 significantly mitigated persistent BHA, while TRIF-deficient mice experienced a faster onset of BHA. Only MIF or HMGB1 inhibition resulted in increased micturition volume. The histopathological examination revealed no changes in inflammation or edema. MIF and HMGB1, acting through TLR4 and RAGE, mediated persistent BHA, while TRIF might modulate its onset. Further exploration of downstream TLR4 signaling may uncover novel therapeutic targets for treating persistent bladder pain.

The oncogenic axis YAP/MYC/EZH2 impairs PTEN tumor suppression activity enhancing lung tumorigenicity

The tumor suppressor PTEN (phosphatase and tensin homolog deleted in chromosome 10) is genetically deleted or downregulated in many cancer types. Loss of PTEN protein expression is frequently found in lung cancer while genetic alterations are less abundant. PTEN expression is regulated at multiple genetic and epigenetic levels and even partial reduction of its expression increases cancer occurrence. We show that YAP and TAZ cooperate with EZH2, and MYC to transcriptionally repress onco-suppressor genes, including PTEN, in non-small cell lung cancer (NSCLC) cells. YAP/TAZ-EZH2-MYC transcriptional regulators form a nuclear complex that represses PTEN transcription, while their combinatorial targeting restores PTEN expression, attenuates NSCLC cell growth, and prevents compensatory responses induced by single treatments. Datasets analysis of NSCLC patients revealed that PTEN expression is negatively correlated to YAP/TAZ, EZH2 and MYC and that low expression of PTEN is predictive of poor prognosis, especially at earlier stages of the disease. These findings highlight the repressive role of the YAP/TAZ-EZH2-MYC axis on tumor-suppressor genes and offer a potential therapeutic strategy for lung cancer patients with low PTEN levels.

Electrochemical boost via thermally reduced graphene oxide for tailoring composite paste electrodes

Carbon-based composite materials are employed in diverse electrochemical applications, such as in catalysis, (bio)molecular sensing, and energy storage. In practice, electrode material needs to be highly conductive to allow high-speed electron transference to electrolyte species and possess high-surface area to obtain greater measured signals and power capabilities, as well as long useful life and stability. In this sense, graphene derivatives emerge as interesting candidates, even more so if they constitute part of practical, economical and versatile paste electrodes.This work presents a detailed analysis of the electrochemical performance of paste electrodes fabricated with multilayer partially reduced graphene oxide (rGO). The rGO was strategically produced via thermal treatment as a key factor that minimizes both mass loss and energy consumption. The results obtained through diffraction, microscopy and spectroscopy techniques show an effective partial reduction in the range of 100 to 400 °C. Furthermore, the enhanced electrochemical performance of rGO was determined by exploring the specific capacitance from cyclic voltammetry (CV) and galvanostatic charge–discharge measurements (GCD) as well as charge transfer resistance via electrochemical impedance spectroscopy (EIS). Our results evidence how an integral performance with suitable chemical, structural and morphological properties achieved for GO heat-treated at 200 °C leads to an improved electronic conductivity when a small part is combined with graphite in paste electrodes. This latter combination provides higher versatility compared to other alternatives since it arises as an economical and effective carbonaceous matrix for (bio)electrochemical sensors, hybrid supercapacitors or other desired nanotechnological applications.

Partial reduction of interleukin-33 signaling improves senescence and renal injury in diabetic nephropathy.

Diabetic nephropathy (DN) is a frequent and costly complication of diabetes with limited understandings of mechanisms and therapies. Emerging evidence points to the important roles of interleukin-33 (IL-33) in acute kidney injury, yet its contribution to DN is still unclear. We here found a ubiquitous increase of IL-33 and its receptor (ST2) in murine models and patients with DN. Surprisingly, both IL-33 and ST2 knockdown aggravated renal lesions in DN, while overexpression of IL-33 also exacerbated the condition. Further population-based analyses revealed a positive correlation of IL-33 expression with renal dysfunction in DN patients. Individuals with high IL-33expression-related polygenic risk score had a higher DN risk. These findings confirmed the harmful effects of IL-33 on DN. Conversely, endogenous and exogenous partial reduction of IL-33 signaling conferred renoprotective effects in vivo and in vitro. Mechanistically, IL-33 induced senescence by regulating cell cycle factors in HK-2 cells, and accordingly senescence led to renal cell damage through the secretion of senescence-related secretory phenotype (SASP) including IL-33 and prostaglandins. Together, elevated IL-33 accelerates cellular senescence to drive DN possibly by SASP production, while a partial blockage improves renal injury and senescence. Our findings pinpoint a possible and new avenue for DN interventions.

Disruption of tRNA biogenesis enhances proteostatic resilience, improves later-life health, and promotes longevity.

tRNAs are evolutionarily ancient molecular decoders essential for protein translation. In eukaryotes, tRNAs and other short, noncoding RNAs are transcribed by RNA polymerase (Pol) III, an enzyme that promotes ageing in yeast, worms, and flies. Here, we show that a partial reduction in Pol III activity specifically disrupts tRNA levels. This effect is conserved across worms, flies, and mice, where computational models indicate that it impacts mRNA decoding. In all 3 species, reduced Pol III activity increases proteostatic resilience. In worms, it activates the unfolded protein response (UPR) and direct disruption of tRNA metabolism is sufficient to recapitulate this. In flies, decreasing Pol III's transcriptional initiation on tRNA genes by a loss-of-function in the TFIIIC transcription factor robustly extends lifespan, improves proteostatic resilience and recapitulates the broad-spectrum benefits to late-life health seen following partial Pol III inhibition. We provide evidence that a partial reduction in Pol III activity impacts translation, quantitatively or qualitatively, in both worms and flies, indicating a potential mode of action. Our work demonstrates a conserved and previously unappreciated role of tRNAs in animal ageing.

High-Coverage Disulfide Mapping Enabled by Programmable Disulfide-Ene Reaction Integrated onto a Bottom-Up Protein Analysis Workflow.

Mapping disulfide linkages is crucial for characterizing pharmaceutical proteins during drug development and quality control. Traditional bottom-up protein analysis workflows often suffer from incomplete mapping for tryptic peptides consisting of multiple disulfide bonds. Although the employment of a partial reduction of disulfide bonds can improve disulfide mapping, it becomes a bottleneck of analysis because individual tuning is often needed. Herein, we have developed an online disulfide-ene reaction system in which the composition of the reaction solvent can be programmed to achieve optimal partial reduction of tryptic disulfide peptides after liquid chromatography separation. By coupling this system onto a bottom-up protein analysis workflow, high coverage for sequencing (71-83%) and disulfide mapping (84-100%) was achieved for standard proteins consisting of 4-19 disulfide bonds. The analytical capability was further demonstrated by mapping 13 scrambled disulfide bonds in lysozyme and achieving compositional analysis of IgG isotypes (κ and λ) and subclasses (IgG1-IgG4) from human plasma.

Alpha- to Beta-Cell Transdifferentiation in Neonatal Compared with Adult Mouse Pancreas in Response to a Modest Reduction in Beta-Cells Using Streptozotocin.

Following the near-total depletion of pancreatic beta-cells with streptozotocin (STZ), a partial recovery of beta-cell mass (BCM) can occur, in part due to the alpha- to beta-cell transdifferentiation with an intermediary insulin/glucagon bi-hormonal cell phenotype. However, human type 2 diabetes typically involves only a partial reduction in BCM and it is not known if recovery after therapeutic intervention involves islet cell transdifferentiation, or how this varies with age. Here, we used transgenic mouse models to examine if islet cell transdifferentiation contributes to BCM recovery following only a partial depletion of BCM. Cell lineage tracing was employed using Glucagon-Cre/yellow fluorescent protein (YFP) transgenic mice treated with STZ (25 mg/kg-neonates; 70 mg/kg-adults) or vehicle alone on 3 consecutive days. Mice were euthanized 2-30 days later with a prior glucose tolerance test on day 30, and immunofluorescence histology performed on the pancreata. Beta-cell abundance was reduced by 30-40% two days post STZ in both neonates and adults, and subsequently partially recovered in adult but not neonatal mice. Glucose tolerance recovered in adult females, but not in males or neonates. Bi-hormonal cell abundance increased 2-3-fold in STZ-treated mice vs. controls in both neonates and adults, as did transdifferentiated cells expressing insulin and the YFP lineage tag, but not glucagon. Transdifferentiated cell presence was an order of magnitude lower than that of bi-hormonal cells. We conclude that alpha- to beta-cell transdifferentiation occurs in mice following only a moderate depletion in BCM, and that this was accompanied by a partial recovery of BCM in adults.

Thermal Transformations in Copper/Sodium-Organosiloxanes of a Globular Structure

The thermal and thermo-oxidative transformations in cage-like metal-organosiloxanes of the general formula [RSiO1.5]12[CuO]4[NaO0.5]4 (R= Ph, Me) were studied. It was established that their decomposition occurs in two stages and includes a number of solid-state reactions, leading to the abstraction of organic groups from the silicon atom, the partial or complete reduction of copper atoms, and the release of metallic and oxide phases.

First description of leucism in the deep-sea angular rough shark (Oxynotus centrina) and the first documented pigment disorder in family Oxynotidae Gill, 1912.

The capture of a rare, critically endangered adult angular rough shark, Oxynotus centrina (Linnaeus, 1758), with abnormal coloration is reported in this paper. The shark exhibited a partial reduction in pigmentation, resulting in an overall pale appearance with white-greyish patches. Since the retinal pigmentation appeared normal, the shark was considered leucistic. This represents the first documented case of leucism in this species and the first colour disorder reported in the family Oxynotidae Gill, 1912. Despite the atypical appearance, the physical health of the shark seemed unaffected, supporting the notion that pigment disorders in deep-sea sharks do not inherently impair survival and growth. Full morphometric characteristics are presented and compared with those of a normal individual of the same sex caught in the same area, showing no differences.

Sodium-Ion Traps in a Two-Dimensional Confined Channel for Effective Water and Ion Selective Transport.

Nanoconfined interlayer channels in two-dimensional (2D) laminates are promising for the construction of novel permselective membranes. Controlling the interlayer spacing and modifying the interlayer chemical microenvironment are effective for high-efficiency separation. However, manipulating ion-diffusion energy barriers in confined channels is challenging, and their role in selective water-ion transport is unclear. This study engineered sodium-ion traps (SITs) in confined graphene oxide (GO) interlayer channels by incorporating N-phenylaza-15-crown-5 (NPCE) to regulate the ion-diffusion energy barriers. Partial reduction of GO enhanced membrane stability and enabled precise adjustment of interlayer spacing, while the addition of NPCE further constricted the free space and entrapped sodium ions by increasing their transport energy barriers. The optimized membrane with NPCE-dominated SITs achieved mono/monovalent-ion efficient sieving (K+/Na+ ≈ 10.2, and Li+/Na+ ≈ 6.7) and rejection of Na2SO4 (∼99.0%) and NaCl (∼90.0%), while maintaining stable performance for >1500 h. The findings provide new insights into manipulating transport energy barriers and modifying other 2D material laminates.

Model Checking Distributed Protocols in Must

We describe the design and implementation of Must, a framework for modeling and automatically verifying distributed systems. Must provides a concurrency API that supports multiple communication models, on top of a mainstream programming language, such as Rust. Given a program using this API, Must verifies it by means of a novel, optimal dynamic partial order reduction algorithm that maintains completeness and optimality for all communication models supported by the API. We use Must to design and verify models of distributed systems in an industrial context. We demonstrate the usability of Must's API by modeling high-level system idioms (e.g., timeouts, leader election, versioning) as abstractions over the core API, and demonstrate Must's scalability by verifying systems employed in production (e.g., replicated logs, distributed transaction management protocols), the verification of which lies beyond the capacity of previous model checkers.

Convenient partial reduction of CO2 to a useful C1 building block: efficient access to 13C‐labelled N‐heterocyclic carbenes

The selective, transition metal‐free hydrosilylation of CO2 to CH2(OSiEt3)2 has been achieved under mild conditions and in high isolated yields (up to 90%) using Et3SiH and the simple, easily prepared borohydride catalyst Li+[HB(C6F5)3]−. The resulting CO2‐derived bis(silyl)acetal product – whose mechanism of formation has been interrogated through detailed computational and experimental studies – can be rapidly valorized through the facile synthesis of N‐heterocyclic carbenes, via their corresponding imidazolium salts. By using relatively inexpensive, isotopically enriched 13CO2 this protocol can be exploited to prepare NHC isotopologues that are selectively 13C labelled at the key, ligating C2 position. This provides an electronically responsive 13C NMR spectroscopic handle with dramatically enhanced sensitivity which can directly benefit reactivity studies in both organo‐ and organometallic catalysis, where NHC use is ubiquitous.

KDELR2 is necessary for chronic obstructive pulmonary disease airway Mucin5AC hypersecretion via an IRE1α/XBP-1s-dependent mechanism.

Airway mucus hypersecretion, a crucial pathological feature of chronic obstructive pulmonary disease (COPD), contributes to the initiation, progression, and exacerbation of this disease. As a macromolecular mucin, the secretory behaviour of Mucin5AC (MUC5AC) is highly dependent on a series of modifying and folding processes that occur in the endoplasmic reticulum (ER). In this study, we focused on the ER quality control protein KDEL receptor (KDELR) and demonstrated that KDELR2 and MUC5AC were colocalized in the airway epithelium of COPD patients and COPD model rats.In addition, knockdown of KDELR2 markedly reduced the expression of MUC5AC both invivo and invitro and knockdown of ATF6 further decreased the levels of KDELR2. Furthermore, pretreatment with 4μ8C, an IRE1α inhibitor, led to a partial reduction in the expression of KDELR2 and MUC5AC both invivo and invitro, which indicated the involvement of IRE1α/XBP-1s in the upstream signalling cascade. Our study revealed that KDELR2 plays a crucial role in airway MUC5AC hypersecretion in COPD, which might be dependent on ATF6 and IRE1α/XBP-1s upstream signalling.

Is Orbital Lobe of the Lacrimal Gland Dispensable? Tear Volume, Ocular Surface, and MRI Volumetric Analysis.

To investigate the effects of lacrimal gland reduction surgeries on the tear volume and ocular surface. This is a cohort study of patients post 2 lacrimal gland reduction surgeries: partial orbital lobe dacryoadenectomy for refractory epiphora (4 patients, mean age: 31 ± 13.6 years, 3 males) and complete orbital lobe dacryoadenectomy for lacrimal gland pleomorphic adenoma (15 patients, mean age: 41 ± 12 years, 7 females). Changes in Schirmer I, ocular surface staining, symptomatology, and lacrimal gland volumetrics (MRI) were assessed before and after the surgical procedure. The median Schirmer value reduction following partial orbital lobe dacryoadenectomy was 5 mm at a mean follow-up of 18 ± 4.9 months. None of them developed dry eye disease or positive ocular staining. The gland volume was reduced by 45.9% to 53.5% in 3 patients and 13.3% in 1 patient. The epiphora improved moderately in 93% of patients. Of 15 patients with lacrimal gland pleomorphic adenoma excision, the median reduction in Schirmer I was 4 mm at a mean follow-up of 12.8 months. Partial or complete removal of the orbital lobe of the lacrimal gland does not induce dry eye disease in otherwise healthy individuals. However, gland volume does not recover following partial reduction, and it seems unlikely that the lacrimal gland regenerates following partial removal.

Photoresponse of Ti3C2Tx MXene promotes its adsorptive-reductive removal of Cr(VI) from water

MXenes, such as Ti3C2Tx, demonstrate tremendous potential as heavy metal adsorbents due to their abundant reaction sites, high hydrophilicity, controllable interlayer spacing, and inherent reduction ability. However, their structural dependent pollutant removal performances and the related mechanisms are far less studied. Therefore, the removing abilities of Cr(VI) from water on Ti3C2Tx MXenes with different structures (multilayer (ML-) and delaminated (DL-) Ti3C2Tx) synthesized via several etching techniques were evaluated. Focusing on the most effective ML- and DL-Ti3C2Tx obtained by acid/fluoride salt etching, the impacts of structural variations on the Cr(VI) removal performances were explored. Both ML- and DL-Ti3C2Tx demonstrate outstanding Cr(VI) adsorption and reduction capabilities, achieving equilibrium within 500 min with capacities of 92.7 and 205 mg/g, respectively. The differences in removal mechanisms stemed from the varying adsorption and reduction capacities of two MXenes. ML-Ti3C2Tx, with lower surface area and porosity, had low adsorption capacity but superior reduction ability, efficiently converting most Cr(VI) to Cr(III) (66.8%). Conversely, DL-Ti3C2Tx exhibited better removal efficiency but a lower capacity for reduction (45.7%). Notably, although the partial reduction of DL-Ti3C2Tx to TiO2 results in its limited chemical reduction capacity, Ti3C2Tx might serve as a co-catalyst for TiO2, boosting the photoresponsiveness of DL-Ti3C2Tx or TiO2 through Ti3C2Tx/TiO2 heterojunctions, thereby facilitating photocatalysis to realize the reduction of Cr(VI). Both Ti3C2Tx exhibited both excellent Cr(VI) removal capacity and detoxification capacity, demonstrating their high potential in treating heavy metal pollutants in wastewater.

Binuclear Coordination Assemblies of Metal Tetraphenylporphyrins (M = Mn, Fe, and In) with Anionic Thioindigo Bridges as Promising Magnetic Systems with Tunable Properties.

A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate trans-thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M-O bonds. Crystalline binuclear assemblies (TI•-)·{[MnIITPP]0·[MnIIITPP]+}·xC6H4Cl2 (x = 2 for 1 or 1 for 2) and (TI2-){[MIIITPP]+}2·xC6H4Cl2 (M = Fe and x = 2 for 3, M = In and x = 1 for 4) were synthesized. The thioindigo (TI2-) dianion and metal (FeIII and InIII) atoms in TPPs maintain their initial charge states during the formation of 3 and 4, allowing the separation of paramagnetic FeIII or diamagnetic InIII ions by a diamagnetic TI2- bridge. Strong antiferromagnetic coupling is observed between FeIII (S = 5/2) centers in complex 3. Partial reduction of MnIII to MnII occurs upon the formation of 1 and 2, leading to assemblies containing three paramagnetic centers: MnII (S = 5/2), MnIII (S = 2), and TI•- radical anion (S = 1/2). Orthogonal arrangement of TPP and TI molecules in 1 provides strong ferromagnetic coupling. Weak antiferromagnetic coupling is realized in 2 due to the rotation of the TI bridge.