MRI-based tumor shrinkage patterns after early neoadjuvant therapy in breast cancer: correlation with molecular subtypes and pathological response after therapy.

BACKGROUND: MRI-based tumor shrinkage patterns (TSP) after neoadjuvant therapy (NAT) have been associated with pathological response. However, the understanding of TSP after early NAT remains limited. We aimed to analyze the relationship between TSP after early NAT and pathological response after therapy in different molecular subtypes. METHODS: We prospectively enrolled participants with invasive ductal breast cancers who received NAT and performed pretreatment DCE-MRI from September 2020 to August 2022. Early-stage MRIs were performed after the first (1st-MRI) and/or second (2nd-MRI) cycle of NAT. Tumor shrinkage patterns were categorized into four groups: concentric shrinkage, diffuse decrease (DD), decrease of intensity only (DIO), and stable disease (SD). Logistic regression analysis was performed to identify independent variables associated with pathologic complete response (pCR), and stratified analysis according to tumor hormone receptor (HR)/human epidermal growth factor receptor 2 (HER2) disease subtype. RESULTS: 344 participants (mean age: 50 years, 113/345 [33%] pCR) with 345 tumors (1 bilateral) had evaluable 1st-MRI or 2nd-MRI to comprise the primary analysis cohort, of which 244 participants with 245 tumors had evaluable 1st-MRI (82/245 [33%] pCR) and 206 participants with 207 tumors had evaluable 2nd-MRI (69/207 [33%] pCR) to comprise the 1st- and 2nd-timepoint subgroup analysis cohorts, respectively. In the primary analysis, multivariate analysis showed that early DD pattern (OR = 12.08; 95% CI 3.34-43.75; p < 0.001) predicted pCR independently of the change in tumor size (OR = 1.37; 95% CI 0.94-2.01; p = 0.106) in HR+/HER2- subtype, and the change in tumor size was a strong pCR predictor in HER2+ (OR = 1.61; 95% CI 1.22-2.13; p = 0.001) and triple-negative breast cancer (TNBC, OR = 1.61; 95% CI 1.22-2.11; p = 0.001). Compared with the change in tumor size, the SD pattern achieved a higher negative predictive value in HER2+ and TNBC. The statistical significance of complete 1st-timepoint subgroup analysis was consistent with the primary analysis. CONCLUSION: The diffuse decrease pattern in HR+/HER2- subtype and stable disease in HER2+ and TNBC after early NAT could serve as additional straightforward and comprehensible indicators of treatment response. TRIAL REGISTRATION: Trial registration at https://www.chictr.org.cn/ . REGISTRATION NUMBER: ChiCTR2000038578, registered September 24, 2020.

Built-In Positive Valence Space Shifting the Chemical Equilibrium Forward for Nitrate Reduction to Ammonia.

The electrochemical conversion of nitrate pollutants into value-added ammonia (NH3) is an appealing alternative synthetic route for sustainable NH3 production. However, the development of the electrocatalytic nitrate-to-ammonia reduction reaction (NO3RR) has been hampered by unruly reactants and products at the interface and the accompanied sluggish kinetic rate. In this work, a built-in positive valence space is successfully constructed over FeCu nanocrystals to rationally regulate interfacial component concentrations and positively shift the chemical equilibrium. With positive valence Cu optimizing the active surface, the space between the stern and shear layers becomes positive, which is able to continuously attract the negatively charged NO3- reactant and repulse the positively charged NH4+ product even under high current density, thus significantly boosting the NO3RR kinetics. The system with a built-in positive valence space affords an ampere-level NO3RR performance with the highest NH3 yield rate of 150.27 mg h-1 mg-1 at -1.3 V versus RHE with an outstanding NH3 current density of 189.53 mA cm-2, as well as a superior Faradaic efficiency (FE) of 97.26% at -1.2 V versus RHE. The strategy proposed here underscores the importance of interfacial concentration regulation and can find wider applicability in other electrochemical syntheses suffering from sluggish kinetics.

Virtual water flows and drivers in the international trade of agricultural products of the regional comprehensive economic partnership.

The regional comprehensive economic partnership (RCEP) is today the largest free trade area in the world. This paper examines agricultural trade in the RCEP from 2010 to 2019 through the perspective of virtual water. And the drivers of the virtual water flow between China and the RCEP are also explored. The results are as follows: the virtual water flow during the study period was 2,576.51 billion m3. From a temporal perspective, the annual virtual water flow over the study period is characterized by a slow rise-significant fall-slow rise. It has the characteristics of concentration in spatial distribution and water resources and product structure. However, the concentration degree showed a downward trend during the study period. Then, we have divided the major trading into four categories based on whether there is a shortage of water on both sides of the trade. In terms of the drivers of virtual water flows between China and the RCEP, we have used the gravity model to arrive at the following findings: crop yields, bilateral economic scale, and agricultural labor resources are the main drivers. Our research results have reference values for adjusting bilateral agricultural trade and water conservation.

The Inhibition Mechanisms of Three Structurally Different Salvianolic Acids on the Non-Enzymatic Glycation of Bovine Serum Albumin.

The antiglycation mechanisms of three structurally different salvianolic acids (Sals) including salvianolic acid A (Sal-A), salvianolic acid B (Sal-B) and salvianolic acid C (Sal-C) were investigated using the bovine serum albumin (BSA)-fructose model. The results showed that the three compounds could inhibit the formation of glycation products, maintain protein structural stability, mitigate the development of amyloid fibrils and scavenge radicals. Notably, Sal-A possessed the highest anti-glycated activity compared with Sal-B and Sal-C. This may be related to the fact that Sal-A contained the most molecules of caffeic acid (Sal-A, Sal-B, and Sal-C possessing two, one, and zero caffeic acid units, respectively), and caffeic acid played a leading role in the antiglycation properties relative to Danshensu. Moreover, these compounds quenched the intrinsic fluorescence intensity of BSA in a static mode, with the binding constants in the order of Sal-A > Sal-B > Sal-C. Obviously, Sal-A possessed the strongest binding affinity among these compounds, which may be one of the reasons why it exhibited the optimal antiglycation capability. Furthermore, molecular docking demonstrated that the three Sals exerted protective effects on BSA by preventing glycation modification of lysine and arginine residues. These findings would provide valuable insights into the potential application of Sals for alleviating non-enzymatic glycation of protein.

Extending Ring-Chain Coupling Empirical Law to Lithium-Mediated Electrochemical Ammonia Synthesis.

With its efficient nitrogen fixation kinetics, electrochemical lithium-mediated nitrogen reduction reaction (LMNRR) holds promise for replacing Haber-Bosch process and realizing sustainable and green ammonia production. However, the general interface problem in lithium electrochemistry seriously impedes the further enhancement of LMNRR performance. Inspired by the development history of lithium battery electrolytes, here, we extend the ring-chain solvents coupling law to LMNRR system to rationally optimize the interface during the reaction process, achieving nearly a two-fold Faradaic efficiency up to 54.78±1.60 %. Systematic theoretical simulations and experimental analysis jointly decipher that the anion-rich Li+ solvation structure derived from ring tetrahydrofuran coupling with chain ether successfully suppresses the excessive passivation of electrolyte decomposition at the reaction interface, thus promoting the mass transfer of active species and enhancing the nitrogen fixation kinetics. This work offers a progressive insight into the electrolyte design of LMNRR system.

Optimizing Intermediate Adsorption over PdM (M=Fe, Co, Ni, Cu) Bimetallene for Boosted Nitrate Electroreduction to Ammonia.

Electrochemical reduction of nitrate to ammonia (NO3RR) is a promising and eco-friendly strategy for ammonia production. However, the sluggish kinetics of the eight-electron transfer process and poor mechanistic understanding strongly impedes its application. To unveil the internal laws, herein, a library of Pd-based bimetallene with various transition metal dopants (PdM (M=Fe, Co, Ni, Cu)) are screened to learn their structure-activity relationship towards NO3RR. The ultra-thin structure of metallene greatly facilitates the exposure of active sites, and the transition metals dopants break the electronic balance and upshift its d-band center, thus optimizing intermediates adsorption. The anisotropic electronic characteristics of these transition metals make the NO3RR activity in the order of PdCu>PdCo≈PdFe>PdNi>Pd, and a record-high NH3 yield rate of 295 mg h-1 mgcat -1 along with Faradaic efficiency of 90.9 % is achieved in neutral electrolyte on PdCu bimetallene. Detailed studies further reveal that the moderate N-species (*NO3 and *NO2) adsorption ability, enhanced *NO activation, and reduced HER activity facilitate the NH3 production. We believe our results will give a systematic guidance to the future design of NO3RR catalysts.

Orderly Coating of Bilayer Polymer to Tailor Microenvironment for Efficient C-N Coupling Toward Highly Selective Urea Electrosynthesis.

Electrosynthesis of urea from co-reduction of carbon dioxide and nitrate is a promising alternative to the industrial process. However, the overwhelming existence of proton and nitrate as well as the insufficient supply of CO2 at the reaction interface usually result in complex product distributions from individual nitrate reduction or hydrogen evolution, instead of C-N coupling. In this work, we systematically optimize this microenvironment through orderly coating of bilayer polymer to specifically tackle the above challenges. Polymer of intrinsic microporosity is chosen as the upper polymer to achieve physical sieving, realizing low water diffusivity for suppressing hydrogen evolution and high gas permeability for smooth mass transfer of CO2 at the same time. Polyaniline with abundant basic amino groups is capable of triggering chemical interaction with acidic CO2 molecules, so that is used as the underlying polymer to serve as CO2 concentrator and facilitate the carbon source supply for C-N coupling. Within this tailored microenvironment, a maximum urea generation yield rate of 1671.6 µg h-1 mg-1 and a high Faradaic efficiency of 75.3% are delivered once coupled with efficient electrocatalyst with neighboring active sites, which is among the most efficient system of urea electrosynthesis.

Bithiophene-Functionalized Infrared Two-Photon Absorption Metal Complexes as Single-Molecule Platforms for Synergistic Photodynamic, Photothermal, and Chemotherapy.

A planar conjugated ligand functionalized with bithiophene and its Ru(II), Os(II), and Ir(III) complexes have been constructed as single-molecule platform for synergistic photodynamic, photothermal, and chemotherapy. The complexes have significant two-photon absorption at 808 nm and remarkable singlet oxygen and superoxide anion production in aqueous solution and cells when exposed to 808 nm infrared irradiation. The most potent Ru(II) complex Ru7 enters tumor cells via the rare macropinocytosis, locates in both nuclei and mitochondria, and regulates DNA-related chemotherapeutic mechanisms intranuclearly including DNA topoisomerase and RNA polymerase inhibition and their synergistic effects with photoactivated apoptosis, ferroptosis and DNA cleavage. Ru7 exhibits high efficacy in vivo for malignant melanoma and cisplatin-resistant non-small cell lung cancer tumors, with a 100 % survival rate of mice, low toxicity to normal cells and low residual rate. Such an infrared two-photon activatable metal complex may contribute to a new generation of single-molecule-based integrated diagnosis and treatment platform to address drug resistance in clinical practice and phototherapy for large, deeply located solid tumors.

Preliminary results of randomized phase II study of etoposide plus lobaplatin or etoposide plus cisplatin with concurrent thoracic radiotherapy in the treatment of limited-stage small cell lung cancer.

The purpose is to compare the clinical efficacy and toxicity of etoposide plus lobaplatin (EL) or etoposide plus cisplatin (EP) with concurrent thoracic radiotherapy during the treatment of limited-stage small cell lung cancer (LS-SCLC). Forty-two patients with LS-SCLC were randomly divided into EL ( n = 19) or EP ( n = 23) regimens combined with thoracic intensity-modulated radiotherapy. The primary endpoint was 1-year progression-free survival (PFS) rate. The 1-, 2-, and 3-year PFS rates in the EL and EP cohorts were 50.8, 38.1, and 12.7%; and 56.5, 43.5, and 29.0%, respectively ( P = 0.527), whereas the 1-, 2-, and 3-year overall survival (OS) rates were 72.2, 52.5, and 43.8%; and 73.9, 48.4, and 48.4%, respectively ( P = 0.923). The hematological toxicities were similar in two cohorts. However, gastrointestinal reactions were more severe in the EP group. The incidence of nausea and vomiting in EL and EP cohorts were 31.6% vs. 73.9% ( P = 0.006) and 20.1% vs. 60.9% ( P = 0.009), respectively. The two cohorts did not show ≥grade 4 radiation esophagitis and ≥grade 3 radiation pneumonitis. The incidence of acute radiation esophagitis in EL group was lower ( P = 0.038), both groups showed a similar incidence of radiation pneumonitis ( P = 1.000). EL or EP chemotherapy with concurrent thoracic radiotherapy showed similar PFS and OS. The EL group showed milder gastrointestinal toxicity and radiation esophagitis. Radiation pneumonitis and hematological toxicity were similar in the two regimens, which can be tolerated by patients.

A covalent crosslinking strategy to construct a robust peptide-based artificial esterase.

Peptide-based artificial enzymes derived from the supramolecular assembly of short peptides have attracted growing attention in recent years. However, the stability of these artificial enzymes is still a problem since their noncovalent supramolecular structure is quite sensitive and frail under environmental conditions. In this study, we reported a covalent crosslinking strategy for the fabrication of a robust peptide-based artificial esterase. Inspired by the di-tyrosine bonds in many natural structural proteins, multi-tyrosines were designed into a peptide sequence with histidine as the catalytic residue for the ester hydrolysis reaction. Upon the photo-induced oxidation reaction, the short peptide YYHYY rapidly transferred into nanoparticle-shaped aggregates (CL-YYHYY) and displayed improved esterase-like catalytic activity than some previously reported noncovalent-based artificial esterases. Impressively, CL-YYHYY showed outstanding reusability and superior stability under high temperature, strong acid and alkaline and organic solvent conditions. This study provides a promising approach to improving the catalytic activity and stability of peptide-based artificial enzymes.

Hollow NiCo2O4-ZnO-Co3O4-/N-C Micro-Cage for Synergistic Bisphenol A Degradation by Activating Persulfate.

The NiCo2O4-ZnO-Co3O4-/N-C micro-cage was successfully synthesized by calcination of the precursor obtained from a hollow ZIF-8/ZIF-67 with nickel nitrate. The preparation process concerning ion exchange and leaching was illustrated by the investigation of the composition and structure of the composites. As a catalyst for the activation of persulfate (PDS) to degrade bisphenol A (BPA), it was discovered that the BPA degradation in the presence of NiCo2O4-Co3O4-ZnO/N-C was more efficient than the solids obtained by ZIF-67 with nickel nitrate, indicated by the sevenfold increase of the apparent reaction rate. The further electrochemical analysis evidenced that the electron transfer was more easily accomplished in the system of BPA-PDS-NiCo2O4-Co3O4-ZnO/N-C. This enhanced activity of NiCo2O4-Co3O4-ZnO/N-C was mainly due to the hollow structure, the synergistic effect of NiCo2O4, as well as the smaller size of the active species, which facilitated the transportation of molecules and ions as well as the activation of PDS.

More-Is-Better Strategy for Constructing Homoligand Polypyridyl Ruthenium Complexes as Photosensitizers for Infrared Two-Photon Photodynamic Therapy.

Photodynamic therapy (PDT) uses a combination of photosensitizers (PSs), light sources, and reactive oxygen species (ROS) to damage only the desired target and keep normal tissues from being hurt. The dark cytotoxicity (chemotoxicity) of PSs, leading to whole-body damage in the absence of irradiation, is a major limiting factor in PDT. How to simultaneously increase ROS generation and decrease dark cytotoxicity is an essential challenge that must be resolved in PS research. In this study, a series of homoligand polypyridyl ruthenium complexes (HPRCs) containing three singlet oxygen (1O2)-generating ligands (L) in a single molecule ([Ru(L)3]2+) have been constructed. Compared to the heteroligand complexes [Ru(bpy)2(L)]2+ where bpy is 2,2'-bipyridine, the 1O2 quantum yield under infrared two-photon irradiation and the DNA photocleavage effect of the HPRCs are significantly enhanced with two more ligands L. The intraligand triplet excited states transition played an important role in the activation of oxygen. The HPRCs target the mitochondria but not the nuclei, generating 1O2 intracellularly under irradiation of visible or infrared light. Ru1 exhibits high phototoxicity and low dark cytotoxicity toward human malignant melanoma cells in vitro. Moreover, HPRCs have minimal cytotoxicity to human normal liver cells, suggesting their potential as antitumor PDT reagents with more security. This study may provide inspiration for the structural design of potent PS for PDT.

Facilitating Reconstruction of the Heterointerface Electronic Structure by the Enriched Oxygen Vacancy for the Oxygen Evolution Reaction.

Exploring high-performance non-precious metal-based electrocatalysts for the sluggish oxygen evolution reaction (OER) process is fundamentally significant for the development of multifarious renewable energy conversion and storage systems. Oxygen vacancy (Vo) engineering is an effective leverage to boost the intrinsic activity of OER, but the underlying catalytic mechanism remains anfractuous. Herein, we realize the construction of oxygen vacancy-enriched porous NiO/ln2O3 nanofibers (designated as Vo-NiO/ln2O3@NFs hereafter) via a facile fabrication strategy for efficient oxygen evolution electrocatalysis. Theoretical calculations and experimental results uncover that, compared with the no-plasma engraving component, the presence of abundant oxygen vacancies in the Vo-NiO/ln2O3@NFs is conducive to modulating the electronic configuration of the catalyst, altering the adsorption of intermediates to reduce the OER overpotential and promote O* formation, upshifting the d band center of metal centers near the Fermi level (Ef), and also increasing the electrical conductivity and enhancing the OER reaction kinetics simultaneously. In situ Raman spectra proclaim that the oxygen vacancy can render the NiO/ln2O3 more easily reconstructible on the surface during the OER course. Therefore, the as-obtained Vo-NiO/ln2O3@NFs demonstrated distinguished OER activity, with an overpotential of only 230 mV at 10 mA cm-2 and excellent stability in alkaline medium, surmounting the majority of the previously reported representative non-noble metal-based candidates. The fundamental insights gained from this work can pave a new path for the electronic structure modulation of efficient, inexpensive OER catalysts via Vo engineering.

Temperature variability and common diseases of the elderly in China: a national cross-sectional study.

BACKGROUND: In the context of climate change, it has been well observed that short-term temperature variability (TV) could increase the overall and cause-specific mortality and morbidity. However, the association between long-term TV and a broader spectrum of diseases is not yet well understood, especially in the elderly. METHODS: Our study used data from the fourth Urban and Rural Elderly Population (UREP) study. Long-term TV was calculated from the standard deviation (SD) of daily minimum and maximum temperatures within the study periods (2010-2014, 2011-2014, 2012-2014, 2013-2014, and 2014). Ten self-reported diseases and conditions were collected by questionnaire, including cataract, hypertension, diabetes, cardio-cerebrovascular diseases, stomach diseases, arthritis, chronic lung disease, asthma, cancer, and reproductive diseases. The province-stratified logistic regression model was used to quantify the association between long-term TV and the prevalence of each disease. RESULTS: A total of 184,047 participants were included in our study. In general, there were significant associations between TV and the prevalence of most diseases at the national level. Cardio-cerebrovascular disease (OR: 1.16, 95% CI: 1.13, 1.20) generated the highest estimates, followed by stomach diseases (OR: 1.15, 95% CI: 1.10, 1.19), asthma (OR: 1.14, 95% CI: 1.06, 1.22), chronic lung diseases (OR: 1.08, 95% CI: 1.03, 1.13), arthritis (OR: 1.08, 95% CI: 1.05, 1.11), and cataract (OR: 1.06, 95% CI: 1.02, 1.10). Moreover, the associations varied by geographical regions and across subgroups stratified by sex, household income, physical activity, and education. CONCLUSIONS: Our study showed that long-term exposure to TV was associated with the prevalence of main diseases in the elderly. More attention should be paid to the elderly and targeted strategies should be implemented, such as an early warning system.

Eliminating Concentration Polarization with Cationic Covalent Organic Polymer to Promote Effective Overpotential of Nitrogen Fixation.

Electrocatalytic nitrogen reduction reaction offers a sustainable alternative to the conventional Haber-Bosch process. However, it is currently restricted by low effective overpotential due to the concentration polarization, which arises from accumulated products, ammonium, at the reaction interface. Here, a novel covalent organic polymer with ordered periodic cationic sites is proposed to tackle this challenge. The whole network exhibits strong positive charge and effectively repels the positively charged ammonium, enabling an ultra-low interfacial product concentration, and successfully driving the reaction equilibrium to the forward direction. With the given potential unchanged, the suppressed overpotential can be much liberated, ultimately leading to a continuous high-level reaction rate. As expected, when this tailored microenvironment is coupled with a transition metal-based catalyst, a 24-fold improvement is generated in the Faradaic efficiency (73.74 %) as compared with the bare one. The proposed strategy underscores the importance of optimizing dynamic processes as a means of improving overall performance in electrochemical syntheses.

Development of SERS-based immunoassay for the detection of cryptococcosis biomarker.

The surface-enhanced Raman scattering (SERS) technique has displayed a broad application prospect in disease diagnosis owing to its high sensitivity, fast responsiveness, and high specificity. In this study, we developed a SERS-based immunoassay for the detection of cryptococcal capsular polysaccharide (glucuronoxylomannan, GXM), which is an important biomarker of cryptococcosis. The coupled localized surface plasmon resonance effect between magnetic SERS substrates and SERS tags gave rise to an enhanced Raman signal upon the formation of sandwich complexes, which contributes to the sensitive and specific detection of GXM. As a result, the developed method provided a lower limit of detection (1.25 ng/mL) than conventional methods, such as latex agglutination, lateral flow assay, and enzyme-linked immunosorbent assay. Additionally, a recovery experiment was performed to detect GXM in human serum, which also validated the potential advantages of a SERS-based immunoassay in the clinical diagnosis of cryptococcosis.

Applications of Red Mud as a Masonry Material: A Review.

Red mud (RM) is a highly alkaline by-product produced by the aluminium industry. The total stockpile of RM in the world is evaluated to be close 4 billion tons, which caused serious soil and water pollution. The use of RM in masonry materials has proven to be a prospective strategy to alleviate the environmental problems caused by RM. During the past decades, various economical treatment methods have been developed for utilization of RM as a masonry material. There are two general categories of products using RM in masonry materials: sintered products and non-sintered products. In this review, the physicochemical properties of RM are introduced, and the different application scenarios for RM in masonry materials are summarized, which is valuable for solving the environmental problems caused by the accumulation of bauxite residue. Moreover, the potential environmental risks of utilizing RM are described. Finally, suggestions for solving the RM problem are proposed.

In vivo Realization of Dual Photodynamic and Photothermal Therapy for Melanoma by Mitochondria Targeting Dinuclear Ruthenium Complexes under Civil Infrared Low-power Laser.

A series of dinuclear RuII complexes with extremely high TPA cross sections in the range of 800-900 nm have been designed. The amphiphilic complex Ru3 containing tert-butyl groups has balanced performance in singlet oxygen generation and photothermal conversion and becomes the ideal drug candidate of the series. Ru3 targets mitochondria without penetrating the nucleus, which substantially increases its photodynamic therapy activity and reduces its dark cytotoxicity. Ru3 successfully suppresses melanoma tumor growth in vitro and in vivo with combined photodynamic and photothermal therapy under low light dose irradiation of an 808 nm low-power laser, avoiding the known PDT resistance in melanoma. The excellent therapeutic effect of Ru3 facilitates its applications in further human trials for larger or deeper buried tumors, thereby becoming a prospective candidate for a new generation of low-power IR-driven dual PDT/PTT drugs.

A disposable gold foil paper-based aptasensor for detection of enteropathogenic Escherichia coli with SERS analysis and magnetic separation technology.

Rapid and sensitive detection of enteropathogenic Escherichia coli (EPEC) in fluids with complex background is an important task for safety quality control in the field of medicine, environment, and food. In this study, a gold foil paper-based aptasensor was developed for the detection of enteropathogenic EPEC O26:K60 with surface-enhanced Raman spectroscopy (SERS) and magnetic separation technology mediated by Fe3O4@Au composite. The gold foil paper was firstly modified with thiolated capture probe and SERS tag. The thiolated aptamer probe for EPEC was immobilized onto a Fe3O4@Au composite. In the presence of EPEC, highly specific recognition between the aptamer probe and EPEC made the Fe3O4@Au composite partially dissociated from the gold foil paper. This led to a decreased Raman intensity response, which showed an obvious negative linear correlation with increasing concentration of EPEC over a wide concentration range from 10 to 107 CFU/mL under an excitation wavelength of 633 nm. The detection limit was about 2.86 CFU/mL in a buffer solution and a licorice extractum and the detection time was only 2.5 h. The results demonstrate that the gold foil paper-based aptasensor can be an excellent biosensing platform that offers a reliable, rapid, and sensitive alternative for EPEC detection.

Coordination-Driven Stereospecific Control Strategy for Pure Cycloisomers in Solid-State Diene Photocycloaddition.

To obtain a pure product without the isomer byproducts is a goal that many chemists are pursuing. As one kind of very important synthesis method, the photochemical reaction is simple and straightforward yet low-selective. In this work, a coordination interaction-based oriented synthesis strategy has been proposed to realize the precise stereochemical control of the isomeric cyclic compounds in the photocycloaddition reaction. Through fixing the reactants via coordination interactions, the arrangements and configurations of the reactants can be adjusted, thereby successfully producing all of the related photocycloaddition products without isomer byproducts for the first time. This work not only provides a new route to synthesize the pure cyclic compounds but also expands the application of the photocycloaddition reaction.