Electrocatalytic Synthesis of Urea: An In-depth Investigation from Material Modification to Mechanism Analysis.

Industrial urea synthesis production uses NH3 from the Haber-Bosch method, followed by the reaction of NH3 with CO2, which is an energy-consuming technique. More thorough evaluations of the electrocatalytic C-N coupling reaction are needed for the urea synthesis development process, catalyst design, and the underlying reaction mechanisms. However, challenges of adsorption and activation of reactant and suppression of side reactions still hinder its development, making the systematic review necessary. This review meticulously outlines the progress in electrochemical urea synthesis by utilizing different nitrogen (NO3 -, N2, NO2 -, and N2O) and carbon (CO2 and CO) sources. Additionally, it delves into advanced methods in materials design, such as doping, facet engineering, alloying, and vacancy introduction. Furthermore, the existing classes of urea synthesis catalysts are clearly defined, which include 2D nanomaterials, materials with Mott-Schottky structure, materials with artificially frustrated Lewis pairs, single-atom catalysts (SACs), and heteronuclear dual-atom catalysts (HDACs). A comprehensive analysis of the benefits, drawbacks, and latest developments in modern urea detection techniques is discussed. It is aspired that this review will serve as a valuable reference for subsequent designs of highly efficient electrocatalysts and the development of strategies to enhance the performance of electrochemical urea synthesis.

Pd(II) and Cu(III) Complexes of Multiply Fused Pentaphyrin Isomers with Tunable Structures and NIR Absorption.

Fused porphyrinoids have received increasing interest in light of their extended conjugation and unique coordination behavior. On the basis of our previously reported multiply fused pentaphyrin isomers 1 and 2, a novel isomer 3 has been synthesized in this work. 3 possesses a hexacyclic fused moiety with a nearly coplanar CCNN cavity involving an inverted pyrrole, which is slightly different from the CNNN ones of 1 and 2 involving an N-confused pyrrole. 1-3 possess cavities with three depronatable protons and thus they all can generate Cu(III) complexes. However, only 3Cu is stable under ambient conditions. On the other hand, 3 remains intact upon treatment with Pd(II) ions, while 1 and 2 could undergo structural rearrangement to accommodate Pd(II), affording 1Pd and 2Pd accompanied by the formation of a lactone ring and the addition of a methoxy group, respectively. Compared with the free bases, the complexes show distinct aromaticity and more intense near-infrared (NIR) absorption up to ca. 1600, 1170, and 1500 nm, respectively. The results indicate that the subtle modification of the linking modes between the pyrrolic units in the fused pentaphyrinoids is effective in modulating the coordination behavior for synthesizing complexes with tunable aromaticity and NIR absorption.

Schizophrenia in the genetic era: a review from development history, clinical features and genomic research approaches to insights of susceptibility genes.

Schizophrenia is a devastating neuropsychiatric disorder affecting 1% of the world population and ranks as one of the disorders providing the most severe burden for society. Schizophrenia etiology remains obscure involving multi-risk factors, such as genetic, environmental, nutritional, and developmental factors. Complex interactions of genetic and environmental factors have been implicated in the etiology of schizophrenia. This review provides an overview of the historical origins, pathophysiological mechanisms, diagnosis, clinical symptoms and corresponding treatment of schizophrenia. In addition, as schizophrenia is a polygenic, genetic disorder caused by the combined action of multiple micro-effective genes, we further detail several approaches, such as candidate gene association study (CGAS) and genome-wide association study (GWAS), which are commonly used in schizophrenia genomics studies. A number of GWASs about schizophrenia have been performed with the hope to identify novel, consistent and influential risk genetic factors. Finally, some schizophrenia susceptibility genes have been identified and reported in recent years and their biological functions are also listed. This review may serve as a summary of past research on schizophrenia genomics and susceptibility genes (NRG1, DISC1, RELN, BDNF, MSI2), which may point the way to future schizophrenia genetics research. In addition, depending on the above discovery of susceptibility genes and their exact function, the development and application of antipsychotic drugs will be promoted in the future.

Hybridization Chain Reaction-Enhanced Biocatalytic Precipitation on Flower-like Bi2S3: Toward Organic Photoelectrochemical Transistor Aptasensing with High Transconductance.

Organic photoelectrochemical transistor (OPECT) bioanalysis has recently emerged as a promising avenue for biomolecular sensing, providing insight into the next-generation of photoelectrochemical biosensing and organic bioelectronics. Herein, this work validates the direct enzymatic biocatalytic precipitation (BCP) modulation on a flower-like Bi2S3 photosensitive gate for high-efficacy OPECT operation with high transconductance (gm), which is exemplified by a prostate-specific antigen (PSA)-dependent hybridization chain reaction (HCR) and subsequent alkaline phosphatase (ALP)-enabled BCP reaction toward PSA aptasensing. It has been shown that light illumination could ideally achieve the maximized gm at zero gate bias, and BCP could efficiently modulate the device's interfacial capacitance and charge-transfer resistance, resulting in a significantly changed channel current (IDS). The as-developed OPECT aptasensor realizes good analysis performance for PSA with a detection limit of 10 fg mL-1. This work features direct BCP modulation of organic transistors and is expected to stimulate further interest in exploring advanced BCP-interfaced bioelectronics with unknown possibilities.

Multiparametric Magnetic Resonance Imaging of the Kidneys: Effects of Regional, Side, and Hydration Variations on Functional Quantifications.

BACKGROUND: To standardize renal functional magnetic resonance imaging (MRI), it is important to understand the influence of side-to-side variation, regional variation within the organ, and hydration states in MRI and to search for variables that are not affected by those variations. PURPOSE: To assess MRI-based biomarkers for characterizing the kidney in healthy volunteers while considering variations in anatomic factors and hydration states. STUDY TYPE: Prospective. SUBJECTS: Twenty-five healthy volunteers (15 females and 10 males, median age 25 years). FIELD STRENGTH/SEQUENCE: 3.0 T intravoxel incoherent motion diffusion-weighted imaging, arterial spinning labeling imaging, blood oxygenation level dependent imaging, and three-dimensional MR elastography. ASSESSMENT: Functional variables were measured before and after water challenge. Regions of interest were manually drawn by two investigators (JC and ZZ, with 8- and 5-year experiences in abdominal radiology) in the cortex, the medulla, and the entire kidney. The medulla/cortex ratio was calculated. STATISTICAL TESTS: Paired t-test or Wilcoxon signed rank test; interobserver correlation coefficient; repeatability coefficients; Spearman's correlation; significance level: P < 0.05. RESULTS: Diffusion parameters were only subject to regional variation. R2*, RBF, and renal stiffness (RS) showed regional variation, side variation, and dependence on hydration states. For each side and hydration state, the cortex showed significantly higher standard apparent diffusion coefficient (sADC), higher true diffusion (D), lower R2*, and lower RS than the medulla. For each region at baseline, the left kidney showed significantly higher R2*, higher RS, and lower renal blood flow (RBF) than the right kidney. For each region and side, RS and RBF increased significantly while R2* decreased significantly after water intake. After introducing the intrinsic regional difference, significantly higher medulla/cortex ratio of RS remained after water intake except for RS@90 Hz in the right kidney. DATA CONCLUSION: Renal multiparametric MRI quantifications were affected by regional variation, side variation, and hydration states. LEVEL OF EVIDENCE: 2 TECHNICAL EFFICACY: Stage 1.

Aromatic Ring-Fused Dipyrrins: Programmed [4 + 2]-Cycloaddition Pathway with Regio-selectivity upon Alkylamino-Substitution.

Sulfolenodipyrrins are employed as building blocks to concisely and efficiently construct aromatic rings (e.g., naphthoquinone, anthraquinone, fullerenes, and phthalimide) from fused dipyrrins by programmed [4 + 2]-cycloaddition reactions. Notably, alkylamino-substitution at the α-position not only enhances the reactivity of sulfolenodipyrrins but also results in the regio-selectivity of the cycloaddition reactions. Theoretical calculations in terms of frontier orbitals of dienes, energy of dienes, steric hindrance, and aromaticity have been conducted to understand the reason in depth. Additionally, the fusion of aromatic groups enables bathochromic absorption with up to ∼130 nm for the monoadducts and to ∼200 nm for the bis-adducts. The phthalimide annulation dipyrrin displays red emission, while the other mono- or bis-adducts do not, owing to the presence of typical acceptors such as quinone analogs or fullerene.

Construction of Zr-Metal-Organic Frameworks-Based Composite Materials toward Anhydrous Proton Conduction and Photocatalytic CO2 Reduction.

Metal-organic frameworks constructed from Zr usually possess excellent chemical and physical stability. Therefore, they have become attractive platforms in various fields. In this work, two families of hybrid materials based on ZrSQU have been designed and synthesized, named Im@ZrSQU and Cu@ZrSQU, respectively. Im@ZrSQU was prepared through the impregnation method and employed for proton conduction. Im@ZrSQU exhibited terrific proton conduction performance in an anhydrous environment, with the highest proton conduction value of 3.6 × 10-2 S cm-1 at 110 °C. In addition, Cu@ZrSQU was synthesized via the photoinduction method for the photoreduction of CO2, which successfully promoted the conversion of CO2 into CO and achieved the CO generation rate of up to 12.4 µmol g-1 h-1. The photocatalytic performance of Cu@ZrSQU is derived from the synergistic effect of Cu NPs and ZrSQU. Based on an in-depth study and discussion toward ZrSQU, we provide a versatile platform with applications in the field of proton conduction and photocatalysis, which will guide researchers in their further studies.

PACAP/PAC1-R activation contributes to hyperalgesia in 6-OHDA-induced Parkinson's disease model rats via promoting excitatory synaptic transmission of spinal dorsal horn neurons.

Pain is a common annoying non-motor symptom in Parkinson's disease (PD) that causes distress to patients. Treatment for PD pain remains a big challenge, as its underlying mechanisms are elusive. Pituitary adenylate cyclase-activating polypeptide (PACAP) and its receptor PAC1-R play important roles in regulating a variety of pathophysiological processes. In this study, we investigated whether PACAP/PAC1-R signaling was involved in the mechanisms of PD pain. 6-hydroxydopamine (6-OHDA)-induced PD model was established in rats. Behavioral tests, electrophysiological and Western blotting analysis were conducted 3 weeks later. We found that 6-OHDA rats had significantly lower mechanical paw withdrawal 50% threshold in von Frey filament test and shorter tail flick latency, while mRNA levels of Pacap and Adcyap1r1 (gene encoding PAC1-R) in the spinal dorsal horn were significantly upregulated. Whole-cell recordings from coronal spinal cord slices at L4-L6 revealed that the frequency of spontaneous excitatory postsynaptic currents (sEPSCs) in dorsal horn neurons was significantly increased, which was reversed by application of a PAC1-R antagonist PACAP 6-38 (250 nM). Furthermore, we demonstrated that intrathecal microinjection of PACAP 6-38 (0.125, 0.5, 2 µg) dose-dependently ameliorated the mechanical and thermal hyperalgesia in 6-OHDA rats. Inhibition of PACAP/PAC1-R signaling significantly suppressed the activation of Ca2+/calmodulin-dependent protein kinase II and extracellular signal-regulated kinase (ERK) in spinal dorsal horn of 6-OHDA rats. Microinjection of pAAV-Adcyap1r1 into L4-L6 spinal dorsal horn alleviated hyperalgesia in 6-OHDA rats. Intrathecal microinjection of ERK antagonist PD98059 (10 µg) significantly alleviated hyperalgesia in 6-OHDA rats associated with the inhibition of sEPSCs in dorsal horn neurons. In addition, we found that serum PACAP-38 concentration was significantly increased in PD patients with pain, and positively correlated with numerical rating scale score. In conclusion, activation of PACAP/PAC1-R induces the development of PD pain and targeting PACAP/PAC1-R is an alternative strategy for treating PD pain.

The preventive effect of dexmedetomidine on anesthesia complications in strabismus surgery: a systematic review and meta-analysis.

OBJECTIVE: Dexmedetomidine is a medication that has analgesic, sedative, and anti-anxiety properties. In the clinical, it is often used to prevent common complications associated with strabismus surgery, including postoperative delirium, postoperative nausea and vomiting, postoperative pain, and oculocardiac reflex. However, its effectiveness and side effects of the present studies are different. The sample sizes of the present studies on the prevention of complications of dexmedetomidine are small. Therefore, this study evaluates the efficacy of dexmedetomidine in preventing anesthesia-related complications in strabismus surgery through a systematic review and meta-analysis. METHODS: Literature was retrieved from 10 commonly used databases and randomized controlled trials published up to May 2022 were sought. The included studies compared the intervention effects of dexmedetomidine versus placebo on anesthesia-related complications in surgery. The occurrence rates of postoperative delirium, postoperative nausea and vomiting, postoperative pain, and oculocardiac reflex in patients undergoing strabismus surgery were evaluated. Statistical analyses and forest plots were generated using Review Manager and STATA software. Binary outcomes were measured using relative risk (RR) with a 95% confidence interval for each outcome. The Cochrane risk of bias tool was used to assess the bias and risk in the studies that met the inclusion criteria. RESULTS: A total of 13 articles were ultimately included in the analysis, comprising 1,018 patients who underwent strabismus surgery. The dexmedetomidine group, compared to the placebo group, demonstrated significant reductions in the incidence of postoperative delirium (RR = 0.73, P = 0.001), severe postoperative delirium (RR = 0.45, P = 0.005), postoperative nausea and vomiting (RR = 0.48, P < 0.0001), and the need for supplemental analgesia postoperatively (RR = 0.60, P = 0.004). Additionally, subgroup analysis revealed that intravenous administration of dexmedetomidine significantly reduced the incidence of oculocardiac reflex (RR = 0.50, P = 0.001). In contrast, intranasal administration of dexmedetomidine did not have a significant effect on the incidence of oculocardiac reflex (RR = 1.22, P = 0.15). There was a significant difference between the subgroups (P = 0.0005, I2 = 91.7%). CONCLUSION: Among patients undergoing strabismus surgery, the use of dexmedetomidine can alleviate postoperative delirium and reduce the incidence of postoperative nausea and vomiting, as well as postoperative pain. Moreover, intravenous administration of dexmedetomidine can lower the occurrence rate of the oculocardiac reflex.

Antiaromatic Sapphyrin Isomer: Transformation into Contracted Porphyrinoids with Variable Aromaticity.

Sapphyrin is a pentapyrrolic expanded porphyrin with a 22π aromatic character. Herein, we report the synthesis of a 20π antiaromatic sapphyrin isomer 1 by oxidative cyclization of a pentapyrrane precursor P5 with a terminal ß-linked pyrrole. The resulting isomer 1, containing a mis-linked bipyrrole unit in the skeleton, exhibits a reactivity for further oxidation due to the distinct antiaromatic electronic structure, affording a fused macrocycle 2, possessing a spiro-carbon-containing [5.6.5.6]-tetracyclic structure. Subsequent treatment with an acid afforded a weakly aromatic pyrrolone-appended N-confused corrole 3, and thermal fusion gave a [5.6.5.7]-tetracyclic-ring-embedded 14π aromatic triphyrin(2.1.1) analog 4. The cyclization at the mis-linked pyrrole moiety of P5 played a crucial role in synthesizing the antiaromatic porphyrinoid susceptible to facile transformation to novel porphyrinoids with variable aromaticity.

Loading Phlorins with Fullerenes by a [4 + 2]-Cycloaddition Reaction: Regulation of the Regioselectivity by Pyrrole Linkage Modes.

Sulfolenopyrrole-based normal and N-confused phlorins have been constructed to address the seldom touched phlorin functionalization and simultaneously explore the effect of the pyrrole linkage modes (αα, αß) on the [4 + 2] cycloaddition reaction. The common sulfolenophlorin 1 contains two sulfolenopyrroles with the same reactivity upon tautomerization and undergoes stepwise [4 + 2]-cycloaddition with fullerene to furnish monoadduct 1-C60 and bisadduct 1-2C60 with a total yield up to 76%. By contrast, the presence of the confused pyrrole in 2 fixes the π-system owing to the low tendency to tautomerize and enables the two sulfolenopyrroles to exhibit in different fashions (i.e., normal NH-type and imino-type). Notably, under milder conditions (120 °C), the monofullerenoadduct 2-C60 forms rapidly and has been isolated from the [4 + 2] cycloaddition reaction of 2 and fullerene as the predominant fraction, accompanied by a trace amount of bisadduct 2-2C60. Raising the temperature to 140 °C did not improve the yield of 2-2C60. The structural analysis of 2-C60 indicates the attachment of fullerene at the iminopyrrole part. The high regioselectivity in the [4 + 2] cycloaddition of the imino-type sulfolenopyrrole unit has been rationalized thermodynamically by the DFT calculation on the relative energy of the two diene intermediates.

Porphyrindiene-Based Tandem Diels-Alder Reaction for Preparing Low-Symmetry π-Extended Porphyrins with Push-Pull Skeletons.

Tandem Diels-Alder reactions of masked porphyrindienes (i.e., sulfolenoporphyrins) with benzoquinones and stilbenes, followed by aromatization, have been developed to load porphyrin with mixed annulation units (i.e., terphenyl and naphthoquinone), furnishing the low-symmetry π-extended porphyrins (DxAy) with push-pull skeletons. All low-symmetrical chromophores display panchromatic absorption spectra, which look like a spectral combination of symmetrical congeners (D4/A4) in a certain ratio. Among them, tD2A2 with trans-arrangement of push/pull units possesses the largest maximum centered at 766 nm with the onset around 900 nm. The fusion of the electron-deficient naphthoquinone moiety on the porphyrin core results in the approximately quantitative regulation of the Eox1 and HOMOs (i.e., 0.10-0.13 V increase for the Eox1 and 0.14-0.16 eV decrease for the HOMOs per naphthoquinone unit). In brief, this work provides a new way to construct low-symmetry π-extended porphyrins with tunable properties resorting to the ratios and locations of the annulated push-pull units.

Hydrogen-assisted synthesis of Ni-ZIF-derived nickel nanoparticle chains coated with nitrogen-doped graphitic carbon layers as efficient electrocatalysts for non-enzymatic glucose detection.

Chains of nickel nanoparticles coated with few nitrogen-doped graphitic carbon layers (Ni@NC) are synthesized by hydrogen-assisted pyrolysis of Ni-ZIF. Hydrogen and temperature can play key roles in the formation of oriented Ni@NC nanoparticle chains, and carbon shells can protect Ni nanoparticles from external oxidation and aggregations. Under the optimized potential (0.60 V vs. Ag/AgCl), the Ni@NC7H nanoparticle chains obtained at 700 °C under H2/Ar atmosphere (Ni@NC7H) demonstrate outstanding performances, such as high sensitivity of 1.44 mA mM-1 cm-2 (RSD = 1.0%), low detection limit of 0.34 µM (S/N = 3), broad linear range from 1 µM to 1.81 mM, and excellent application potential in artificial sweat and human serum. Therefore, the findings above indicate that this study will provide a general methodology for the synthesis of chains-like core-shell nanoparticle electrocatalysts for non-enzymatic glucose detection.

Expanded N-Confused Phlorin: A Platform for a Multiply Fused Polycyclic Ring System via Oxidation within the Macrocycle.

Novel interrupted π-conjugated macrocycles derived from expanded porphyrinoids were synthesized, and their unique reactivity was investigated in this work. The specific porphyrin analogs, so-called phlorins and isoporphyrins, possess a meso-sp3 methylene moiety, showing inner 3NH and 1NH pyrrolic cores, respectively, and extended near-infrared (NIR) absorption. Expanded N-confused pentapyrrolic phlorin analog 1 bears an interrupted cyclic π-conjugated system that is featured by a distinct higher HOMO and a lower LUMO. Oxidation of 1 allowed structural transformations through the expanded isoporphyrin-like species 2. One of the representative products is a spiro-carbon-bridged multiply N-fused product 3 comprising a fused [5.6.5.7.6.5]-hexacyclic ring obtained by oxidation with 2,3-dichloro-5,6-dicyano-p-benzoquinone. When magic blue was used as the oxidant, an aromatic N-confused pentaphyrin 4 was obtained via migration of one of the meso-phenyl groups to the ß-position of the neighboring pyrrolic ring. By employing the flexible cavity of 1 for metal coordination, Pd(II) complexation occurred with a specific meso oxygenation to give a bimetallic complex 5. In contrast to the rich oxidation reactions, reduction of 1 with NaBH4 resulted in the regioselective nucleophilic hydrogen substitution reaction at the para position of one of the meso-C6F5 groups. These results provide a practical approach for synthesizing novel interrupted or aromatic π-conjugated frameworks showing NIR absorptions.

Developing an Online Measurement Device Based on Resistance Sensor for Measurement of Single Grain Moisture Content in Drying Process.

The online measurement of moisture content for grains is an essential technology to realize real-time tracking and control, improve drying quality and reduce energy consumption of the drying process. To improve the measurement accuracy and reliability of the dynamic measurement process as well as expand the application scope of the device, the present work constructed an experimental equipment for determining dynamic resistance characteristics of a single grain. The relations between moisture content and real-time resistance waveform were revealed, and an analytical calculation method of peak value and peak area of waveform was proposed, which correctly revealed the electrical measurement properties of grain. The results demonstrated that the gap width between the electrodes had large influence on the sensor's performance. Moreover, an online measuring device was developed based on the experimental analysis and calculation method, and the test results in both lab and field for different grains showed that online real-time absolute measurement error are within ±0.5% in the varied moisture content (10-35%w.b.) and the temperature (-20-50 °C). The main results and the developed device might provide technical support for developing intelligent grain drying equipment.

Exergoeconomic Analysis of Corn Drying in a Novel Industrial Drying System.

The improvement of the design and operation of energy conversion systems is a theme of global concern. As an energy intensive operation, industrial agricultural product drying has also attracted significant attention in recent years. Taking a novel industrial corn drying system with drying capacity of 5.5 t/h as a study case, based on existing exergoeconomic and exergetic analysis methodology, the present work investigated the exergetic and economic performance of the drying system and identified its energy use deficiencies. The results showed that the average drying rate for corn drying in the system is 1.98 gwater/gdry matter h. The average exergy rate for dehydrating the moisture from the corn kernel is 345.22 kW and the exergy efficiency of the drying chamber ranges from 14.81% to 40.10%. The average cost of producing 1 GJ exergy for removing water from wet corn kernels is USD 25.971, while the average cost of removing 1 kg water is USD 0.159. These results might help to further understand the drying process from the exergoeconomic perspective and aid formulation of a scientific index for agricultural product industrial drying. Additionally, the results also indicated that, from an energy perspective, the combustion chamber should be firstly optimized, while the drying chamber should be given priority from the exergoeconomics perspective. The main results would be helpful for further optimizing the drying process from both energetic and economic perspectives and provide new thinking about agricultural product industrial drying from the perspective of exergoeconomics.

N-Confused Phlorin-Prodigiosin Chimera: meso-Aryl Oxidation and π-Extension Triggered by Peripheral Coordination.

An N-confused phlorin isomer bearing a dipyrrin moiety at the α-position of the confused pyrrole ring (1) was synthesized. PdII and BIII coordination at the peripheral prodigiosin-like moiety of 1 afforded the corresponding complexes 2 and 3. Reflux of 2 in triethylamine (TEA) converted the meso-phenyl into the PdII -coordinating phenoxy group to afford 4. Under the same reaction conditions, TEA was linked to the α-position of the dipyrrin unit in 3 as an N,N-diethylaminovinyl group to afford 5. Furthermore, peripheral coordination of BIII in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of AgIII at the inner cavity to afford 3-Ag and 5-Ag, respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination.

Regioselectively Halogenated Expanded Porphyrinoids as Building Blocks for Constructing Porphyrin-Porphyrinoid Heterodyads with Tunable Energy Transfer.

Expanded porphyrins have been attracting increasing attention owing to their unique optical and electrochemical properties as well as switchable aromaticity. Toward material applications, regioselective functionalization of the expanded porphyrins at their periphery is indeed challenging due to the presence of multiple reactive sites. Herein, a set of regioselective halogenated isomers (L5-Br-A/B/C) of neo-confused isosmaragdyrin (L5) are synthesized by a combination of the halogenation reaction of L5 and sequential macrocycle-to-macrocycle transformation reactions of its halogenated isomers. On this basis, the regioselectively functionalized isosmaragdyrins are utilized as building blocks for constructing multichromophoric porphyrinoids, specifically, heterodyads L5-ZnP-A/B/C, in which a common zinc porphyrin is linked at three different pyrrolic positions of isosmaragdyrins, respectively, by Sonogashira coupling reactions. The highly efficient energy cascade from porphyrin to isosmaragdyrin is elucidated using steady-state/time-resolved spectroscopies and theoretical calculations. Notably, the energy transfer processes from the porphyrin to the isosmaragdyrin moieties as well as the excitation energy transfer rates in L5-ZnP-A/B/C are highly dependent on the linking sites by through-bond and Förster-type resonance energy transfer mechanisms. The site-selective functionalization and subsequent construction of a set of heterodyads of the expanded porphyrinoid would provide opportunities for developing new materials for optoelectronic applications.

Yellow Dioxobilin-Type Tetrapyrroles from Chlorophyll Breakdown in Higher Plants-A New Class of Colored Phyllobilins.

In senescent leaves chlorophyll (Chl) catabolites typically accumulate as colorless tetrapyrroles, classified as formyloxobilin-type (or type-I) or dioxobilin-type (type-II) phyllobilins (PBs). Yellow type-I Chl catabolites (YCCs) also occur in some senescent leaves, in which they are generated by oxidation of colorless type-I PBs. A yellow type-II PB was recently proposed to occur in extracts of fall leaves of grapevine (Vitis vinifera), tentatively identified by its mass and UV/Vis absorption characteristics. Here, the first synthesis of a yellow type-II Chl catabolite (DYCC) from its presumed natural colorless type-II precursor is reported. A homogenate of a Spatiphyllum wallisii leaf was used as "green" means of effective and selective oxidation. The synthetic DYCC was fully characterized and identified with the yellow grapevine leaf pigment. As related yellow type-I PBs do, the DYCC functions as a reversible photoswitch by undergoing selective photo-induced Z/E isomerization of its C15=C16 bond.

Computational study of aromaticity, 1H NMR spectra and intermolecular interactions of twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives.

The recently synthesized twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives have been studied computationally. Gauge-including magnetically induced current calculations predict a global nonaromatic character of the initial thia-norhexaphyrin due to the highly-twisted conformation of the macrocycle. Upon the oxidation of the thia-norhexaphyrin four multiply annulated polypyrrolic aromatic macrocycles are formed for which the global aromatic character is confirmed in agreement with experimentally measured 1H NMR spectra. The calculation of the proton chemical shifts for the studied compounds by direct comparison with the tetramethylsilane standard leads to a significant mean absolute error. At the same time a linear regression procedure for the two selected groups of protons (CH and NH protons) provides much better values of calculated chemical shifts and tight correlation with experiment. The separate consideration of NH protons is motivated by the numerous intermolecular hydrogen bonds in which the protons are involved, which induce considerable upfield shifts, leading to a significant underestimation of the corresponding chemical shifts. Such a selected correlation can be used for accurate estimation of proton chemical shifts of the related porphyrinoids. Bader's theory of Atoms in Molecules has been applied for the studied twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives to characterize intramolecular H-bonds and other non-covalent interactions.