Record release of tetramethylguanidine using a green light activated photocage for rapid synthesis of soft materials.

Photocages have enabled spatiotemporally governed organic materials synthesis with applications ranging from tissue engineering to soft robotics. However, the reliance on high energy UV light to drive an often inefficient uncaging process limits their utility. These hurdles are particularly evident for more reactive cargo, such as strong organobases, despite their attractive potential to catalyze a range of chemical transformations. Herein, two metal-free boron dipyrromethene (BODIPY) photocages bearing tetramethylguanidine (TMG) cargo are shown to induce rapid and efficient polymerizations upon exposure to a low intensity green LED. A suite of spectroscopic characterization tools were employed to identify the underlying uncaging and polymerization mechanisms, while also determining reaction quantum efficiencies. The results are directly compared to state-of-the-art TMG-bearing ortho-nitrobenzyl and coumainylmethyl photocages, finding that the present BODIPY derivatives enable step-growth polymerizations that are >10× faster than the next best performing photocage. As a final demonstration, the inherent multifunctionality of the present BODIPY platform in releasing radicals from one half of the molecule and TMG from the other is leveraged to prepare polymers with starkly disparate physical properties. The present findings are anticipated to enable new applications of photocages in both small-molecule photochemistry for medicine and advanced manufacturing of next generation soft materials.

Boron-Methylated Dipyrromethene as a Green Light Activated Type I Photoinitiator for Rapid Radical Polymerizations.

Unimolecular (Type I) radical photoinitiators (PIs) have transformed the chemical manufacturing industry by enabling (stereo)lithography for microelectronics and emergent 3D printing technologies. However, the reliance on high energy UV-violet light (≤420 nm) restricts the end-use applications. Herein, boron-methylated dipyrromethene (methylated-BODIPY) is shown to act as a highly efficient Type I radical PI upon irradiation with low energy green light. Using a low intensity (∼4 mW/cm2) light emitting diode centered at 530 nm and a low PI concentration (0.3 mol %), acrylic-based resins were polymerized to maximum conversion in ∼10 s. Under equivalent conditions (wavelength, intensity, and PI concentration), state-of-the-art visible light PIs Ivocerin and Irgacure 784 show no appreciable polymerization. Spectroscopic characterization suggests that homolytic ß-scission at the boron-carbon bond results in radical formation, which is further facilitated by accessing long-lived triplet excited states through installment of bromine. Alkylated-BODIPYs represent a new modular visible light PI platform with exciting potential to enable next generation manufacturing and biomedical applications where a spectrally discrete, low energy, and thus benign light source is required.

Coupling angle tolerance of the 850-nm single-mode VCSEL output collimated by lensed OM4-MMF or GI-SMF for a NRZ-OOK link.

By collimating the single-mode (SM) vertical-cavity surface-emitting laser (VCSEL) at 850 nm with either the OM4 multi-mode fiber (OM4-MMF) or the graded-index single-mode fiber (GI-SMF) with lensed end-face, the directly encoded non-return-to-zero on-off keying (NRZ-OOK) data transmission performance is characterized when tilting the coupling angle with respect to the surface normal of the SM-VCSEL. In comparison with the lensed OM4-MMF and lensed SMF coupling, the lensed OM4-MMF collimator shows a large coupling angle tolerance with the coupling efficiency only degraded by 5% when enlarging the tilted angle from 0° to 10°. In contrast, the lensed GI-SMF collimator attenuates the coupled SM-VCSEL output by more than 50% when tilting the coupling angle up to 10°. For the lensed OM4-MMF coupling, the receivable NRZ-OOK data rate in BtB and after 100-m OM4-MMF cases can achieve 50 Gbit/s with its corresponding BER degraded from 6.5 × 10-10 to 8.8 × 10-10 when enlarging its tilting angle ranged from 0° to 10°. By changing the collimator to the lensed SMF, the decoded BER significantly degrades from 5.8 × 10-5 to 1.2 × 10-1 when coupling and transmitting the NRZ-OOK data at 50 Gbit/s. Owing to the low coupling efficiency via the lensed SMF collimator, the error-free NRZ-OOK data rate under the lensed SMF coupling somewhat decreases to 35 Gbit/s in the BtB link and to 32 Gbit/s after the 100-m GI-SMF link with allowable coupling angle tilted from 0° to 4°. This work confirms the applicability of the lensed MMF or SMF collimator for coupling the SM-VCSEL output with a relatively large tolerance on the tilting angle with respect to the surface normal of the SM-VCSEL.

Rapid hydrogel formation via tandem visible light photouncaging and bioorthogonal ligation.

The formation of benign polymer scaffolds in water using green-light-reactive photocages is described. These efforts pave an avenue toward the fabrication of synthetic scaffolds that can facilitate the study of cellular events for disease diagnosis and treatment. First, a series of boron dipyrromethene (BODIPY) photocages with nitrogen-containing nucleophiles were examined to determine structure-reactivity relationships, which resulted in a >1,000× increase in uncaging yield. Subsequently, photoinduced hydrogel formation in 90 wt % water was accomplished via biorthogonal carbonyl condensation using hydrophilic polymer scaffolds separately containing BODIPY photocages and ortho-phthalaldehyde (OPA) moieties. Spatiotemporal control is demonstrated with light on/off experiments to modulate gel stiffness and masking to provide <100 µm features. Biocompatability of the method was shown through pre-/post-crosslinking cell viability studies. Short term, these studies are anticipated to guide translation to emergent additive manufacturing technology, which, longer term, will enable the development of 3D cell cultures for tissue engineering applications.

Comparing the Ion-Conducting Polymers with Sulfonate and Ether Moieties as Cathode Binders for High-Power Lithium-Ion Batteries.

Two types of ion-conducting polyimides with sulfonate or ether functional groups were synthesized as ion-type or coordination-type cathode binders for lithium-ion batteries (LIBs), respectively. Although superior ion transport abilities have been reported for both types of ion-conducting polymers, their electrochemical performances are significantly different and the corresponding transport mechanisms at the electrolyte/electrode interface remain elusive. Here, we combine experimental and computational techniques to investigate the cathode interface in the presence of both functional polymer binders in comparison with the poly(vinylidene fluoride) (PVDF) binder as reference. A broad shoulder in the cyclic voltammogram accompanied by a poor rate performance of battery tests was observed for a LiFePO4 cathode with coordination-type ether-based polyimide (EPI) binder. In contrast, a LiFePO4 cathode with ion-type sulfonated polyimide (SPI) binder exhibits smaller concentration polarization, achieving satisfactory capacity at high current density. Simulations show that the ether-based binder strongly coordinates Li ions and thus slows the diffusion of Li ions. This leads to the reduction of the LIB electrochemical performance at a high C-rate. In contrast, the negative moiety of the SPI binder leads to less localization of Li ions, allowing a slightly higher Li-ion mobility. Conventional PVDF shows no affinity to Li ions, leading to less Li-ion accumulation at the electrode/electrolyte interface. Yet, the cathode surface covered with PVDF shows the lowest Li-ion diffusivity compared to those with the two types of Li-ion-conducting binders. Therefore, cathodes with SPI and PVDF binders show less polarization at the electrode interface and allow higher C-rate performance of LIBs. The combined results provide a comprehensive understanding of the mechanism of ion conduction in ion- and coordination-type Li-ion-conducting polymer binders. This gives valuable insight into the design of next-generation polymer materials for high-power LIBs.

Catalyst Halogenation Enables Rapid and Efficient Polymerizations with Visible to Far-Red Light.

The driving of rapid polymerizations with visible to near-infrared light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. The improvement of efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to far-red light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (<1 mW/cm2) and catalyst loadings (<50 µM), exemplified by reaction completion within 60 s of irradiation using green, red, and far-red light-emitting diodes. Halogenated BODIPY photoredox catalysts were additionally employed to produce complex 3D structures using high-resolution visible light 3D printing, demonstrating the broad utility of these catalysts in additive manufacturing.

High-stability inorganic perovskite quantum dot-cellulose nanocrystal hybrid films.

Inorganic perovskite quantum dots (IPQDs) such as cesium lead halide (CsPbX3, X = Cl, Br and I) quantum dots have attracted much attention for developing cadmium-free quantum light-emitting displays (QLEDs) based on outstanding light emission properties including narrow full width at half maximum (FWHM), tunable bandgap and ultrahigh (>90%) photoluminescence quantum yield (PLQY). Nevertheless, their poor stability under ambient conditions, at high temperature or under continuous light irradiation is the main problem for practical applications. In this study, a new method is proposed to effectively stabilize CsPbBr3 IPQDs by synthesizing them with sulfate-functionalized cellulose nanocrystals (CNCs) at room temperature without using traditional quantum dot stabilizers such as oleylamine (OLA) and oleic acid (OA). The as-prepared CsPbBr3 IPQD/CNC hybrid paper-like films are highly stable and the relative photoluminescence (PL) intensity can be maintained at 92% under continuous UV light (306 nm, 15 W) illumination for 130 h, >99% at high temperature (100 °C) for 130 h, and >99% in ambient conditions for 15 d. Additionally, the PLQY and FWHM of IPQD/CNC are 45.69% and 22 nm, respectively. The ultrahigh stability and narrow FWHM characteristics proposed here for IPQD/CNC hybrid films can provide new possibilities for practical applications in the future development of IPQD-related devices.

Effects of Cholesterol on Water Permittivity of Biomimetic Ion Pair Amphiphile Bilayers: Interplay between Membrane Bending and Molecular Packing.

Ion pair amphiphile (IPA), a molecular complex composed of a pair of cationic and anionic amphiphiles, is an inexpensive phospholipid substitute to fabricate vesicles with various pharmaceutical applications. Modulating the physicochemical and permeation properties of IPA vesicles are important for carrier designs. Here, we applied molecular dynamics simulations to examine the cholesterol effects on the structures, mechanics, and water permittivity of hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS) and dodecyltrimethylammonium- hexadecylsulfate (DTMA-HS) IPA bilayers. Structural and mechanical analyses indicate that both IPA systems are in gel phase at 298 K. Adding cholesterol induces alkyl chain ordering around the rigid sterol ring and increases the cavity density within the hydrophilic region of both IPA bilayers. Furthermore, the enhanced alkyl chain ordering and the membrane deformation energy induced by cholesterol increase the permeation free energy penalty. In contrast, cholesterol has minor effects on the water local diffusivities within IPA membranes. Overall, the cholesterol reduces the water permittivity of rigid IPA membranes due to the synergistic effects of increased alkyl chain ordering and enhanced membrane mechanical modulus. The results provide molecular insights into the effects of molecular packing and mechanical deformations on the water permittivity of biomimetic IPA membranes, which is critical for designing IPA vesicular carriers.

Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts.

Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh3 /Cl (b), PPh3 /CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC6 F5 and I2 C6 F4 ). Compounds 1 a and 2 a (L/Y=DMSO/Cl) afford the adducts 1 a⋅⋅⋅I2 C6 F4 and 2 a⋅⋅⋅I2 C6 F4 , which feature I⋅⋅⋅Sbtpy /I⋅⋅⋅πbtpy and I⋅⋅⋅ODMSO /I⋅⋅⋅Cl short contacts, respectively. The phosphane-cyanide derivatives 1 c and 2 c (L/Y=PPh3 /CN) co-crystallise with both IC6 F5 and I2 C6 F4 . None of the phpy-based species 3 a-3 c participated in XB interactions. Although the native complexes are rather poor luminophores in the solid state (Φem =0.023-0.089), the adducts exhibit an up to 10-fold increase of the intensity with a minor alteration of the emission energy. The observed gain in the quantum efficiency is mainly attributed to the joint influence of non-covalent interactions (halogen/hydrogen bonding, π-π stacking), which govern the crystal-packing mode and diminish the radiationless pathways for the T1 →S0 transition by providing a rigid environment around the chromophore.

Laser absorption spectroscopy data processing method based on co-frequency and dual-wavelength and its application.

In the detection process of atmospheric laser absorption spectroscopy in open space, the transmitted beam is inevitably affected by atmospheric turbulence, resulting in superimposed fluctuation noise in the received optical signal. First, the correction method of atmospheric turbulence is theoretically analyzed. In order to reduce the error influence factors and the error transfer coefficient, a new method of spectral data processing based on co-frequency and dual-wave has been proposed. By modifying scintillation noise and background noise, the influence of atmospheric turbulence noise in open space is reduced. An atmospheric detection system in open space based on co-frequency and dual-wave has been established. The experimental results show that the maximum fluctuation of the spectral signal processed by the method of spectrum data processing based on the co-frequency and dual-wave is reduced from 12.854% to 4.635%, and the single-intensity absorbance is fitted by Voigt with its correlation coefficient of 0.9525. The mean of the standard deviation of the algorithm is 0.1370, while the mean value of the standard deviation of the existing algorithm in a short time is 0.6928. And, through the comparative experiment, the standard deviation of the existing data processing techniques of two-wavelength differential absorption is 0.2974, while the standard deviation of the method of spectrum data processing based on the co-frequency and dual-wave is 0.1038. It can be concluded that the co-frequency and dual-wave method can effectively reduce the influence of atmospheric turbulence noise and laser flashing to improve the stability of concentration measurement, which has practical engineering value.

The Excited-State Triple Proton Transfer Reaction of 2,6-Diazaindoles and 2,6-Diazatryptophan in Aqueous Solution.

3-Me-2,6-diazaindole ((2,6-aza)Ind) was strategically designed and synthesized to probe water molecule catalyzed excited-state proton transfer in aqueous solution. Upon electronic excitation (λmax ∼ 300 nm), (2,6-aza)Ind undergoes N(1)-H to N(6) long-distance proton transfer in neutral H2O, resulting in normal (340 nm) and proton-transfer tautomer (480 nm) emissions with an overall quantum yield of 0.25. The rate of the water-catalyzed proton transfer shows a prominent H/D kinetic isotope effect, which is determined to be 8.3 × 108 s-1 and 4.7 × 108 s-1 in H2O and D2O, respectively. Proton inventory experiments indicate the involvement of two water molecules and three protons, which undergo a relay type of excited-state triple proton transfer (ESTPT) in a concerted, asynchronous manner. The results demonstrate for the first time the fundamental of triple proton transfer in pure water for azaindoles as well as pave a new avenue for 2,6-diazatryptophan, an analogue of tryptophan exhibiting a similar ESTPT property with (2,6-aza)Ind, to probe biowaters in proteins.

Room-temperature phosphorescence from small organic systems containing a thiocarbonyl moiety.

Small organic molecules based on the unnatural DNA base pair dTPT3 are designed and synthesized, among which compounds bearing the thiocarbonyl group, compared with their carbonyl counterparts, show a much larger SOC integral between S1(1nπ*) and T1(3ππ*) states due to the appropriate energy level alignment and the heavy sulfur atom effect, resulting in the appearance of both fluorescence and phosphorescence in solution and solid state at room temperature.

Cyclometalated Platinum(II) Cyanometallates: Luminescent Blocks for Coordination Self-Assembly.

A family of cyanide-bridged heterometallic aggregates has been constructed of the chromophoric cycloplatinated metalloligands and coordinatively unsaturated d10 fragments {M(PPh3)n}. The tetranuclear complexes of general composition [Pt(C^N)(CN)2M(PPh3)2]2 [C^N = ppy, M = Cu (1), Ag (2); C^N = tolpy (Htolpy = 2-(4-tolyl)-pyridine), M = Cu (4), Ag (5); C^N = F2ppy (HF2ppy = 2-(4, 6-difluorophenyl)-pyridine), M = Cu (7), Ag (8)] demonstrate a squarelike arrangement of the molecular frameworks, which is achieved due to favorable coordination geometries of the bridging ligands and the metal ions. Variation of the amount of the ancillary phosphine (for M = Ag) afforded compounds [Pt(C^N)(CN)2Ag(PPh3)]2 (C^N = ppy, 3; C^N = tolpy, 6); for the latter one an alternative cluster topology, stabilized by the Pt-Ag metallophilic and η1-Cipso(C^N)-Ag bonding, was observed. The solid-state structures of all of the title species 1-8 were determined crystallographically. The complexes exhibit moderately strong room-temperature phosphorescence as crystalline powders (Φem = 16-34%, λem = 470-511 nm). The luminescence studies and time-dependent density functional theory computational analysis indicate that the photophysical behavior is dominated by the 3π-π* electronic transitions localized on the cyclometalated fragment and mixed with MPtLCT contribution, while the d10-phosphine motifs have a negligible contribution into the frontier orbitals and therefore show a little influence on the emission performance of the described compounds.

N-H-Type Excited-State Proton Transfer in Compounds Possessing a Seven-Membered-Ring Intramolecular Hydrogen Bond.

A series of compounds containing 5-(2-aminobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (o-ABDI) as the core chromophore with a seven-membered-ring N-H-type intramolecular hydrogen bond have been synthesized and characterized. The acidity of the N-H proton and thus the hydrogen-bond strength can be fine-tuned by replacing one of the amino hydrogen atoms by a substituent R, the acidity increasing with increasing electron-withdrawing strength of R, that is, in the order H

Ambipolar Phosphine Derivatives to Attain True Blue OLEDs with 6.5% EQE.

A family of new branched phosphine derivatives {Ph2N-(C6H4)n-}3P → E (E = O 1-3, n = 1-3; E = S 4-6, n = 1-3; E = Se 7-9, n = 1-3; E = AuC6F5 4-6, n = 1-3), which are the donor-acceptor type molecules, exhibit efficient deep blue room temperature fluorescence (λem = 403-483 nm in CH2Cl2 solution, λem = 400-469 nm in the solid state). Fine tuning the emission characteristics can be achieved varying the length of aromatic oligophenylene bridge -(C6H4)n-. The pyramidal geometry of central R3P → E fragment on the one hand disrupts π-conjugation between the branches to preserve blue luminescence and high triplet energy, while on the other hand provides amorphous materials to prevent excimer formation and fluorescence self-quenching. Hence, compounds 2, 3, 5, and 12 were used as emitters to fabricate nondoped and doped electroluminescent devices. The luminophore 2 (E = O, n = 2) demonstrates excellently balanced bipolar charge transport and good nondoped device performance with a maximum external quantum efficiency (EQEmax) of 3.3% at 250 cd/m(2) and Commission International de L'Eclairage (CIE) coordinates of (0.15, 0.08). The doped device of 3 (E = O, n = 3) shows higher efficiency (EQEmax of 6.5, 6.0 at 100 cd/m(2)) and high color purity with CIE (0.15, 0.06) that matches the HDTV standard blue. The time-resolved electroluminescence measurement indicates that high efficiency of the device can be attributed to the triplet-triplet annihilation to enhance generation of singlet excitons.

Effects of insulin-like growth factor 1 receptor and its inhibitor AG1024 on the progress of lung cancer / 华中科技大学学报（医学）（英德文版）

The type 1 insulin-like growth factor receptor (IGF-1R) and its downstream signaling components have been increasingly recognized to drive the development of malignancies, including non-small cell lung cancer (NSCLC). This study aimed to investigate the effects of IGF-1R and its inhibitor, AG1024, on the progression of lung cancer. Tissue microarray and immunohistochemistry were employed to detect the expressions of IGF-1 and IGF-1R in NSCLC tissues (n=198). Western blotting was used to determine the expressions of IGF-1 and phosphorylated IGF-1R (p-IGF-1R) in A549 human lung carcinoma cells, and MTT assay to measure cell proliferation. Additionally, the expressions of IGF-1, p-IGF-1R and IGF-1R in a mouse model of lung cancer were detected by Western blotting and real-time fluorescence quantitative polymerase chain reaction (FQ-PCR), respectively. The results showed that IGF-1 and IGF-1R were overexpressed in NSCLC tissues. The expression levels of IGF-1 and p-IGF-1R were significantly increased in A549 cells treated with IGF-1 as compared to those treated with IGF-1+AG1024 or untreated cells. In the presence of IGF-1, the proliferation of A549 cells was significantly increased. The progression of lung cancer in mice treated with IGF-1 was significantly increased as compared to the group treated with IGF-1+AG1024 or the control group, with the same trend mirrored in IGF-1/p-IGF-1R/IGF-1R at the protein and/or mRNA levels. It was concluded that IGF-1 and IGF inhibitor AG1024 promotes lung cancer progression.

CLINICAL ANALYSIS OF STRESS FRACTURE OF THE PUBIC RAMUS CAUSED BY MILITARY TRAINING: A REPORT OF 66 CASES / 解放军医学杂志

To investigate the clinical diagnosis and treatment of stress fracture of the pubic ramus caused by military training, clinical data of 66 cases (18 males and 48 females, ranging from 18～21 years, mean age 19 6 years ) with stress fracture of the pubic ramus were retrospectively analysed. 55 cases were military recruits undergoing basic training, 11 army veterans undergoing intensive goose step training. 66 cases complained of chronic groin pain which increased in activity and relieved while at rest. The symptom occurred 3～10 weeks after the training began. The pain often lasted 1 week ～14 months. 22 cases who sought medical advice in medical team were mistaken for muscular injury. There were 76 stress fractures of the pubic ramus in 66 soldiers. 56 had stress fractures of one inferior pubic ramus, 6 both inferior pubic rami, and four had ipsilateral inferior and superior pubic rami fractures. Stress fracture of the pubic ramus is not rare, but it's quite easy to be neglected or misdiagnosed. The key to its diagnosis is getting a deeper understanding and making an adequate and early imaging examination in light of the clinical data.

X-ray diagnosis of stress fracture of the pubic ramus / 中华放射学杂志

Objective To study the X-ray findings and evaluate the value of X-ray in diagnosis of stress fracture of the pubic ramus. Methods The X-ray findings of 66 cases (18 males and 48 females, ranging in age from 18-21 years, mean age 19.6 years) with stress fracture of the pubic ramus were retrospectively analyzed. Fifty-five cases were military recruits undergoing basic training, and 11 army veterans were undergoing intensive goose step training. Results Sixty-two cases had stress fractures of the inferior pubic ramus including right-sided in 26, left-sided in 30, and bilateral in 6. Four had ipsilateral inferior and superior pubic rami fractures. With 2 weeks after onset, the radiographs were normal in 3 cases. The 66 cases had either a slight transverse fissure (34 cases) or a small dense callus (65 cases) or both during the examination period of 4 weeks to 8 months. Then the calcium resorbed at the margins of the fracture and at the same time the callus increased and surrounded the bone. Finally, the resorptive zone disappeared and the callus became homogeneous. This callus formation persisted for several months and disappeared gradually. Conclusion X-ray examination is the first imaging method of choice for detecting stress fracture of the pubic ramus. With combining clinical data, correct diagnosis can be made in the majority.

Reevaluation of the importance of finding rash, lymphadenitis and eschars for the early clinical diagnosis of Tsutsugamushi disease / 감염

No abstract available.