Open Isomer Research Articles

Effects of different processing methods on phenolic compounds in flaxseed meal

This study examined effects of different processing methods on phenolic compounds in flaxseed meal. The optimal SE treatment was 1.0 MPa for 3 min, and the contents of total flavonoids and phenolic acid were 2.26 times and 1.63 times of the control group, respectively. Notably, erucic acid increased 85.76 %. Optimal extrusion conditions (15 % moisture content, 140 °C, 29 hz) led to the presence of rutin and a 2.81 times increase in protocatechuic acid content over the control. Fermenting with 3 % Bacillus subtilis for 4 days yielded gallic acid in bound form and vanillic acid in free form, with protocatechuic acid increasing 40.65 % compared to the control. Among all the treatments, extrusion produced the highest levels of phenolic compounds in flaxseed meal. Each treatment significantly increased the open ring isomer ester phenol (SDG) compared to the control. Overall, various processing methods impacted the phenolic content and composition in flaxseed meal differently.

Advanced Structure Analysis Reveals a Transient Portimine B Hydrate.

Portimine B was isolated from an extract derived from the dinoflagellate Vulcanodinium rugosum, a known producer of the closely related portimine A. Initial molecular characterization studies of portimine B suggested an open tetrahydrofuranyl ring isomer, contrary to the intact ring moiety found in portimine A. In 2023, the Baran lab synthesized both portimines A and B suggesting that both macrocyclic analogs contained the intact tetrahydrofuranyl ring. In this note, we utilize newly acquired NMR data, the i-HMBC NMR experiment, and advanced density functional theory calculations to define the structural divergence, originating from the presence of a transient hydrate.

Revisiting fulgide photochromism: Mechanistic decoding and electron transport from computational exploration.

The photochromic behavior of the fulgide molecule relies on ring-closure and ring-opening processes involving conical intersections during excited state transformation between isomers. The precise location and topography of these conical intersections significantly shape the decay process and fluorescence phenomena inherent to the molecule. This work combines electronic structure theory calculations using the density functional theory and wavefunction methods, as well as surface hopping simulation to analyze the photochemical behavior of an experimentally synthesized fulgide molecule, (E)-p-methylacetophenylisopropylidenesuccinic anhydride (1E). Our study reveals the conical intersection between the first excited state (S1) and the ground electronic state (S0), which emerges beyond the S1 minimum of 1E to the ring-closing side. The distinctive topography of this conical intersection appears to be sloped. These findings suggest a reduced quantum yield for the formation of the closed isomer, indicating a higher likelihood of reformation of the open isomer(s). The surface hopping simulation further supports this observation, revealing a mere ∼8% quantum yield for the formation of the closed isomer. In addition, the photoisomerization of the fulgide molecule initiates a cascade of conduction switching and holds great potential for applications in molecular electronics. Delving into the realm of molecular electronics, we have further examined the electron transport properties, disclosing the higher conductivity of the closed isomer.

Ion-Cross-Linked Hybrid Photochromic Hydrogels with Enhanced Mechanical Properties and Shape Memory Behaviour.

Shape-shifting polymers usually require not only reversible stimuli-responsive ability, but also strong mechanical properties. A novel shape-shifting photochromic hydrogel system was designed and fabricated by embedding hydrophobic spiropyran (SP) into double polymeric network (DN) through micellar copolymerisation. Here, sodium alginate (Alg) and poly acrylate-co-methyl acrylate-co-spiropyran (P(SA-co-MA-co-SPMA)) were employed as the first network and the second network, respectively, to realise high mechanical strength. After being soaked in the CaCl2 solution, the carboxyl groups in the system underwent metal complexation with Ca2+ to enhance the hydrogel. Moreover, after the hydrogel was exposed to UV-light, the closed isomer of spiropyran in the hydrogel network could be converted into an open zwitterionic isomer merocyanine (MC), which was considered to interact with Ca2+ ions. Interestingly, Ca2+ and UV-light responsive programmable shape of the copolymer hydrogel could recover to its original form via immersion in pure water. Given its excellent metal ion and UV light stimuli-responsive and mechanical properties, the hydrogel has potential applications in the field of soft actuators.

Photoswitchable optoelectronic properties of 2D MoSe2/diarylethene hybrid structures

The ability to modulate optical and electrical properties of two-dimensional (2D) semiconductors has sparked considerable interest in transition metal dichalcogenides (TMDs). Herein, we introduce a facile strategy for modulating optoelectronic properties of monolayer MoSe2 with external light. Photochromic diarylethene (DAE) molecules formed a 2-nm-thick uniform layer on MoSe2, switching between its closed- and open-form isomers under UV and visible irradiation, respectively. We have discovered that the closed DAE conformation under UV has its lowest unoccupied molecular orbital energy level lower than the conduction band minimum of MoSe2, which facilitates photoinduced charge separation at the hybrid interface and quenches photoluminescence (PL) from monolayer flakes. In contrast, open isomers under visible light prevent photoexcited electron transfer from MoSe2 to DAE, thus retaining PL emission properties. Alternating UV and visible light repeatedly show a dynamic modulation of optoelectronic signatures of MoSe2. Conductive atomic force microscopy and Kelvin probe force microscopy also reveal an increase in conductivity and work function of MoSe2/DAE with photoswitched closed-form DAE. These results may open new opportunities for designing new phototransistors and other 2D optoelectronic devices.

Intramolecular excimers of open forms of 2H-benzopyran, 2H- and 3H-naphthopyrans in solution: TD-DFT/DFT analysis.

We hypothesized that in the open forms of diphenyl-substituted photochromic compounds, immediately after the photoinduced cleavage of the C-O bond, one of the phenyl rings forms a stack with an aromatic system at the other end of the alkyl linker. The formation of these intramolecular stacking excimers is made possible by a known increase in the rotational mobility of the linker double bonds in the excited state. The flexibilities of linkers are analyzed in terms of changes in their dihedral angles. After internal conversion, stacking is partially broken but it still prevents the recovery of the C-O bond. This explains the significantly greater stability of the open forms of diphenyl-substituted benzopyran and naphthopyran compared to dimethyl-substituted ones. Open structures with residual stacking are intermediate and by thermal motion, they transform into stable trans-trans and cis-trans forms. However, in our opinion, they significantly affect the equilibrium of closed and open isomers in solution. In particular, the calculated stacking energy of 2H-naphthopyran turned out to be higher than that of 3H-naphthopyran, which partly explains the significantly greater stability of the open form of the former. For the DFT/TD-DFT calculations performed in this work, the following functionals were selected to provide reliable stacking for the open forms of all three studied compounds: APFD, M052X, M06HF, as well as B3LYP with D3(BJ) Grimme dispersion correction. The 6-311++G(d,p) basis set and cyclohexane solvent modeled using IEFPCM were also used.

Theoretical Study of the Photocyclization Reaction-Induced Dual Aggregation-Induced Emission Phenomenon.

Photochromic molecules with aggregation-induced emission (AIE) effects are of great value and prospective in various practical applications. To explore its inherent mechanism, the open isomer ap-BBTE and the closed isomer c-BBTE were chosen to perform the theoretical calculation using the quantum mechanics/molecular mechanics model combined with thermal vibration correlation function formalism. The calculations show that the photocyclization (PC) reaction from ap-BBTE to c-BBTE facilitates an improvement in the AIE effect. It is found that the fluorescence quantum yield (ΦF) enhancement of ap-BBTE is attributed to the restriction of the low-frequency rotational motion of the benzothiophene moiety and the high-frequency stretching vibrations of the C-C bond between the benzothiophene and benzylbis(thiadiazole) vinyl groups after aggregation. For c-BBTE, the increase in ΦF upon aggregation is mainly due to the suppression of the high-frequency stretching vibration of the C-C bond between the benzothiophene and the benzobis(thiadiazole) vinyl groups. In addition, the AIE effect was also enhanced from ap-BBTE to c-BBTE, which is consistent with the experimental phenomenon. The corresponding emission spectrum red-shifted from ap-BBTE to c-BBTE in both dilute solution and the crystalline state due to the improved intramolecular conjugation of c-BBTE. Moreover, the PC reaction from ap-BBTE to c-BBTE easily occurs in an excited state with a low energy barrier transition state by forming a C-C bond between benzothiophene groups effectively in dilute solution. Our calculations provide theoretical guidance for the further rational design of efficient AIE luminogens.

Frequency-dependent nonlinear optical response and refractive index investigation of lactone-derived thermochromic compounds

Nonlinear optical (NLO) switchable materials play a crucial role in the fields of electronics and optoelectronics. The selection of an appropriate switching approach is vital in designing such materials to enhance their NLO response. Among various approaches, thermos-switching materials have shown a 4-fold increase in NLO response compared to other photo-switching materials. In this study, we computationally investigated the geometric, electronic, and nonlinear optical properties of reversible lactone-based thermochromic compounds using the ωB97XD/6-311+G (d,p) level of theory. Molecular orbital studies are employed to analyze the electronic properties of the close and open isomers of these compounds, while time-dependent density functional theory (TD-DFT) analysis is utilized to evaluate their molecular absorption. Our findings reveal that the π-electronic conjugation-induced delocalization significantly influences the ON-OFF switchable nonlinear optical response of the lactone-based thermochromic compounds. Notably, among all compounds, the open isomer of lactone 2 exhibits the highest hyperpolarizability value (6596.69 au). Furthermore, we extended our analysis to investigate the frequency-dependent second and third-order hyperpolarizabilities. The most pronounced frequency-dependent NLO response is observed at 532 nm. Additionally, we calculated the refractive index of these thermochromic compounds to further assess their nonlinear optical response. The open isomer of lactone 1 demonstrates the highest refractive index value (3.99 × 10−14 cm2/W). Overall, our study highlights the excellent potential of reversible thermochromic compounds as NLO molecular thermos-switches for future applications.

Role of Delocalization, Asymmetric Distribution of π-Electrons and Elongated Conjugation System for Enhancement of NLO Response of Open Form of Spiropyran-Based Thermochromes.

Switchable nonlinear optical (NLO) materials have widespread applications in electronics and optoelectronics. Thermo-switches generate many times higher NLO responses as compared to photo-switches. Herein, we have investigated the geometric, electronic, and nonlinear optical properties of spiropyranes thermochromes via DFT methods. The stabilities of close and open isomers of selected spiropyranes are investigated through relative energies. Electronic properties are studied through frontier molecular orbitals (FMOs) analysis. The lower HOMO-LUMO energy gap and lower excitation energy are observed for open isomers of spiropyranes, which imparts the large first hyperpolarizability value. The delocalization of π-electrons, asymmetric distribution and elongated conjugation system are dominant factors for high hyperpolarizability values of open isomers. For deep understanding, we also analyzed the frequency-dependent hyperpolarizability and refractive index of considered thermochromes. The NLO response increased significantly with increasing frequency. Among all those compounds, the highest refractive index value is observed for the open isomer of the spiropyran 1 (1.99 × 10-17 cm2/W). Molecular absorption analysis confirmed the electronic excitation in the open isomers compared to closed isomers. The results show that reversible thermochromic compounds act as excellent NLO molecular switches and can be used to design advanced electronics.

Non-Conjugated Bis-(Dithienylethene)-Naphthalenediimide as a Dynamic Anti-Counterfeiting Agent: Driving the Wheel of Photoswitching Enactment.

Photochromic fluorescent molecules dramatically extend their fields of applications ranging from optical memories, bioimaging, photoswitches, photonic devices, anti-counterfeiting technology and many more. Here, we have logically designed and synthesized a triazole appended bis-(dithienylethene)-naphthalenediimide based photo-responsive material, 5, which demonstrated fluorescence enhancement property upon photocyclization (ΦF =0.42), with high photocyclization (44 s, ksolution =0.0355 s-1 , ksolid =0.0135 s-1 ) and photocycloreversion (160 s, ksolution =0.0181 s-1 , ksolid =0.0085 s-1 ) rate and decent photoreaction quantum yield (Φo→c =0.93 and Φc→o =0.11). The open isomer almost converted to the closed isomer at photo-stationary state (PSS) with distinct color change from colorless to blue with 92.85 % conversion yield. A reversible noninvasive modulation of fluorescence through efficient photoinduced electron transfer (PET) process was observed both in solution as well as in solid state. The fluorescence modulation through PET process was further corroborated with thermodynamic calculations using the Rehm-Weller equation and quantum chemical studies (DFT). The thermally stable compound 5 exhibits high fatigue resistance property (up to 50 cycles) both in solution and solid state. Furthermore, the compound 5 was successfully applied as erasable ink and in deciphering secret codes (Quick Response/bar code) portending potential promising application in anti-counterfeiting.

All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields.

Molecular systems and devices whose properties can be modulated using light as an external stimulus are the subject of numerous research studies in the fields of materials and life sciences. In this context, the use of photochromic compounds that reversibly switch upon light irradiation is particularly attractive. However, for many envisioned applications, and in particular for biological purposes, illumination with harmful UV light must be avoided and these photoactivable systems must operate in aqueous media. In this context, we have designed a benzo[e]-fused dimethyldihydropyrene compound bearing a methyl-pyridinium electroacceptor group that meets these requirements. This compound (closed state) is able to reversibly isomerize under aerobic conditions into its corresponding cyclophanediene form (open isomer) through the opening of its central carbon-carbon bond. Both the photo-opening and the reverse photoclosing processes are triggered by visible light illumination and proceed with high quantum yields (respectively 14.5% yield at λ = 680 nm and quantitative quantum yield at λ = 470 nm, in water). This system has been investigated by nuclear magnetic resonance and absorption spectroscopy, and the efficient photoswitching behavior was rationalized by spin-flip time-dependent density functional theory calculations. In addition, it is demonstrated that the isomerization from the open to the closed form can be electrocatalytically triggered.

Efficient blue light-responsed dithienylethenes with exceptional photochromic performance

Three novel dithienylethenes modified by bifluoroboron β-diketonate fragments have been successfully developed. Upon blue light irradiation, they reached photostationary state within 2–5 s, as well as 100% conversion ratio and photocyclization quantum yield of > 0.70. Such fascinating photochromism were endowed by collaborative role of electron-withdrawing effect of BF2bdk group to reduce HOMO-LUMO electronic gap for the open isomer, together with intramolecular hydrogen bonds and CH-π interactions favoring antiparallel conformation fixation. Moreover, they displayed specific discrimination and photoswitchable bacterial imaging for S. aureus.

Influence of periodic heteroatom substitution in the aryl rings on optical properties and thermal stability of diarylethene derivatives

Photochromic diarylethene derivatives are one of the most promising candidates for various applications in optoelectronic devices. The heteroatom substitution of the aryl groups of diarylethene derivatives could greatly influence their optical properties and thermal stability. For example, the diarylethene derivatives with two thiophene rings (Dithienylethenes) have longer absorption wavelength, better fatigue resistance, sensitivity and thermal bistability than those with two furan rings. To further understand the influence of the heteroatom substitution in aryl rings, a series of diarylethene derivatives with different heteroatoms in IV (C, Si, Ge), V (N, P, As), and VI groups (O, S, Se) of Periodic Table were theoretically explored with DFT/TD-DFT functionals. According to the predicted results, the substituent effects of increasing atomic weights could influence the optical properties, the relative energies, the thermal bistability of the open isomer and the closed isomers. The maximum optical absorptions of the closed isomers and the open isomers could be finely tuned by these heteroatom groups in visible region of 395∼522 nm and in ultraviolet region of 300∼341 nm, respectively. The diarylethene with Se substituent diarylethene was predicted to have the best thermal bistability of all the nine substitutions and also have comparable photochomic properties than widely-used S diarylethene (Dithienylethenes). As 6π-electron system is indispensable part for nearly all known diarylethene derivates, the study probably provides a useful guideline for the future design of novel Se substituent diarylethene compounds with tunable photochromic properties and improved thermal bistability.

Regioselective CF2 functionalization of Sc3N@D3h(5)-C78

CF2 addition to Sc3N@D3h(5)-C78 proceeds regioselectively and much readier than to Sc3N@C80. The resulting Sc3N@C78(CF2) is a kinetically controlled closed product considerably less favorable energetically than several alternative open isomers.

Cover Feature: Photoresponsive Binding Dynamics in High‐Affinity Cucurbit[8]uril‐Dithienylethene Host‐Guest Complexes (Chem. Eur. J. 37/2021)

Photoresponsive binding kinetics was achieved in cucurbit[8]uril-dithienylethene host-guest complexes. This work demonstrates that, in the presence of a competitor guest (in purple), the host-guest dissociation kinetics is approximately 100-fold slower for the closed (green) than for the open (yellow) dithienylethene isomers (t 1/2=107 hours vs. t 1/2=1.2 hours), allowing control over the dissociation rate with red/NIR light. More information can be found in the Full Paper by A. Jorge Parola, N. Basílio, et al. (DOI: 10.1002/chem.202100974).

Light-Triggered Metal Coordination Dynamics in Photoswitchable Dithienylethene-Ferrocene System.

The C2-symmetric photochromic molecule 3, containing dithienylethene (DTE) and ferrocene units connected by an alkyne bridge, represents a unique probe where a metal (Hg2+) binds with the central DTE moiety. Both photoisomerized states of 3 (open, 3o; closed, 3c) are found to interact with Hg2+ ion by the S atoms of the DTE core; however, the binding constants (from a UV-vis study) and DFT calculations suggest that the open isomer (3o) binds with the metal ion more strongly than that of the closed isomer (3c). Notably, the course of metal binding does not perturb the inherent photoisomerization properties of the DTE core and the photoswitchability persists even in the metal-coordinated form of 3, however, with a comparatively slower rate. The quantum yields for photocyclization (Φo→c) and photocycloreversion (Φc→o) in the free form are 0.56 and 0.007, respectively, whereas the photocyclization quantum yield in the Hg2+ complexed species is 0.068, 8.2 times lower than the photocyclization quantum yield (Φo→c) of free 3o. Thus, the rate of photoisomerization can be modulated by a suitable metal coordination to the DTE core. The dynamics of photoswitchability in the metal-coordinated form of DTE has been explored by experimental means (UV-vis and electrochemical studies) as well as quantum chemical calculations.

Diarylethene-Powered Light-Induced Folding of Supramolecular Polymers.

Helical folding of randomly coiled linear polymers is an essential organization process not only for biological polypeptides but also for synthetic functional polymers. Realization of this dynamic process in supramolecular polymers (SPs) is, however, a formidable challenge because of their inherent lability of main chains upon changing an external environment that can drive the folding process (e.g., solvent, concentration, and temperature). We herein report a photoinduced reversible folding/unfolding of rosette-based SPs driven by photoisomerization of a diarylethene (DAE). Temperature-controlled supramolecular polymerization of a barbiturate-functionalized DAE (open isomer) in nonpolar solvent results in the formation of intrinsically curved, but randomly coiled, SPs due to the presence of defects. Irradiation of the randomly coiled SPs with UV light causes efficient ring-closure reaction of the DAE moieties, which induces helical folding of the randomly coiled structures into helicoidal ones, as evidenced by atomic force microscopy and small-angle X-ray scattering. The helical folding is driven by internal structure ordering of the SP fiber that repairs the defects and interloop interaction occurring only for the resulting helicoidal structure. In contrast, direct supramolecular polymerization of the ring-closed DAE monomers by temperature control affords linearly extended ribbon-like SPs lacking intrinsic curvature that are thermodynamically less stable compared to the helicoidal SPs. The finding represents an important concept applicable to other SP systems; that is, postpolymerization (photo)reaction of preorganized kinetic structures can lead to more thermodynamically stable structures that are inaccessible directly through temperature-controlled protocols.

Promoting the Furan Ring‐Opening Reaction to Access New Donor–Acceptor Stenhouse Adducts with Hexafluoroisopropanol

AbstractDonor–acceptor Stenhouse adducts (DASAs) are visible‐light‐responsive photoswitches with a variety of emerging applications in photoresponsive materials. Their two‐step modular synthesis, centered on the nucleophilic ring opening of an activated furan, makes DASAs readily accessible. However, the use of less reactive donors or acceptors renders the process slow and low yielding, which has limited their development. We demonstrate here that 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) promotes the ring‐opening reaction and stabilizes the open isomer, allowing greatly reduced reaction times and increased yields for known derivatives. In addition, it provides access to previously unattainable DASA‐based photoswitches and DASA–polymer conjugates. The role of HFIP and the photochromic properties of a set of new DASAs is probed using a combination of 1H NMR and UV/Vis spectroscopy. The use of sterically hindered, electron‐poor amines enabled the dark equilibrium to be decoupled from closed‐isomer half‐lives for the first time.

Promoting the Furan Ring-Opening Reaction to Access New Donor-Acceptor Stenhouse Adducts with Hexafluoroisopropanol.

Donor–acceptor Stenhouse adducts (DASAs) are visible‐light‐responsive photoswitches with a variety of emerging applications in photoresponsive materials. Their two‐step modular synthesis, centered on the nucleophilic ring opening of an activated furan, makes DASAs readily accessible. However, the use of less reactive donors or acceptors renders the process slow and low yielding, which has limited their development. We demonstrate here that 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) promotes the ring‐opening reaction and stabilizes the open isomer, allowing greatly reduced reaction times and increased yields for known derivatives. In addition, it provides access to previously unattainable DASA‐based photoswitches and DASA–polymer conjugates. The role of HFIP and the photochromic properties of a set of new DASAs is probed using a combination of 1H NMR and UV/Vis spectroscopy. The use of sterically hindered, electron‐poor amines enabled the dark equilibrium to be decoupled from closed‐isomer half‐lives for the first time.

Constructing photochromic diarylethene with NIR-absorption beyond 800 nm

Near-infrared (NIR) absorbing dyes have received increasing attention due to their ability of NIR radiation absorption and efficient light-to-heat conversion. NIR absorbing photochromic diarylethene (DAE) materials, which could modulate NIR absorption upon light stimulation, provide a convenient route to fabricate smart NIR absorbers. In this study, we constructed a new NIR absorbing photochromic DAE system, of which NIR absorption stems from closed isomer bearing triarylamine (TAA) radical (TDEc-ox). Upon 365/440 nm light irradiation, the open isomer TDEo undergoes photo-oxidation and cyclization to yield TDEc-ox, which exhibited NIR absorption at 928 nm in chloroform. TDEc-ox possesses a photo-inactive feature facilitating non-destructive readout of NIR absorption and high stability (lifetime time ≥ 3 days). Contrary to TDEo, the closed isomer TDEc cannot be directly photo-oxidized to give TDEc-ox. This discrepancy makes TDEc a “photogenerated TAA radical reservoir”: after cycles of photoisomerization, a controllable accumulation of NIR absorbing TDEc-ox can be achieved.