Elucidating the structural changes of cellulose molecules and dynamics of Na ions during the crystal transition from cellulose I to II in low temperature and low concentration NaOH solution.

Low-concentration alkali treatments at low temperatures facilitate the crystal transition of cellulose I to II. However, the transition mechanism remains unclear. Hence, in this study, we traced the transition using in situ solid-state 13C CP/MAS NMR, WAXS, and 23Na NMR relaxation measurements. In situ solid-state 13C CP/MAS NMR and WAXS measurements revealed that soaking cellulose in NaOH at low temperatures disrupts the intramolecular hydrogen bonds and lowers the crystallinity of cellulose. The dynamics of Na ions (NaOH) play a crucial role in causing these phenomena. 23Na NMR relaxation measurements indicated that the Na-ion correlation time becomes longer during the crystal transition. This transition requires the penetration of Na ions (NaOH) into the cellulose crystal and a reduction in Na-ion mobility, which occurs at low temperatures or high NaOH concentrations. The interactions between cellulose and NaOH disrupt intramolecular hydrogen bonds, inducing a conformational change in the cellulose molecules into a more stable arrangement. This weakens the hydrophobic interactions of cellulose, and facilitates the penetration of NaOH and water into the crystal, leading to the formation of alkali cellulose. Our findings suggest that a strategy to control NaOH dynamics could lead to the discovery of a novel preparation method for cellulose II.

Thermoresponsive Property of Poly(N,N-bis(2-methoxyethyl)acrylamide) and Its Copolymers with Water-Soluble Poly(N,N-disubstituted acrylamide) Prepared Using Hydrosilylation-Promoted Group Transfer Polymerization.

The group-transfer polymerization (GTP) of N,N-bis(2-methoxyethyl)acrylamide (MOEAm) initiated by Me2EtSiH in the hydrosilylation-promoted method and by silylketene acetal (SKA) in the conventional method proceeded in a controlled/living manner to provide poly(N,N-bis(2-methoxyethyl)acrylamide) (PMOEAm) and PMOEAm with the SKA residue at the α-chain end (MCIP-PMOEAm), respectively. PMOEAm-b-poly(N,N-dimethylacrylamide) (PDMAm) and PMOEAm-s-PDMAm and PMOEAm-b-poly(N,N-bis(2-ethoxyethyl)acrylamide) (PEOEAm) and PMOEAm-s-PEOEAm were synthesized by the block and random group-transfer copolymerization of MOEAm and N,N-dimethylacrylamide or N,N-bis(2-ethoxyethyl)acrylamide. The homo- and copolymer structures affected the thermoresponsive properties; the cloud point temperature (Tcp) increasing by decreasing the degree of polymerization (x). The chain-end group in PMOEAm affected the Tcp with PMOEAmx > MCIP-PMOEAmx. The Tcp of statistical copolymers was higher than that of block copolymers, with PMOEAmx-s-PDMAmy > PMOEAmx-b-PDMAmy and PMOEAmx-s-PEOEAmy > PMOEAmx-b-PEOEAmy.

Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene).

The redox behaviors of macrocyclic molecules with an entirely π-conjugated system are of interest due to their unique optical, electronic, and magnetic properties. In this study, defect-free cyclic P3HT with a degree of polymerization (DPn) from 14 to 43 was synthesized based on our previously established method, and its unique redox behaviors arising from the cyclic topology were investigated. Cyclic voltammetry (CV) showed that the HOMO level of cyclic P3HT decreases from -4.86 eV (14 mer) to -4.89 eV (43 mer), in contrast to the linear counterparts increasing from -4.94 eV (14 mer) to -4.91 eV (43 mer). During the CV measurement, linear P3HT suffered from electro-oxidation at the chain ends, while cyclic P3HT was stable. ESR and UV-Vis-NIR spectroscopy suggested that cyclic P3HT has stronger dicationic properties due to the interactions between the polarons. On the other hand, linear P3HT showed characteristics of polaron pairs with multiple isolated polarons. Moreover, the dicationic properties of cyclic P3HT were more pronounced for the smaller macrocycles.

Photon extraction enhancement of praseodymium ions in gallium nitride nanopillars.

Lanthanoid-doped Gallium Nitride (GaN) integrated into nanophotonic technologies is a promising candidate for room-temperature quantum photon sources for quantum technology applications. We manufactured praseodymium (Pr)-doped GaN nanopillars of varying size, and showed significantly enhanced room-temperature photon extraction efficiency compared to unstructured Pr-doped GaN. Implanted Pr ions in GaN show two main emission peaks at 650.3 nm and 651.8 nm which are attributed to 3P0-3F2 transition in the 4f-shell. The maximum observed enhancement ratio was 23.5 for 200 nm diameter circular pillars, which can be divided into the emitted photon extraction enhancement by a factor of 4.5 and the photon collection enhancement by a factor of 5.2. The enhancement mechanism is explained by the eigenmode resonance inside the nanopillar. Our study provides a pathway for Lanthanoid-doped GaN nano/micro-scale photon emitters and quantum technology applications.

A case of pancreatic duct stones treated with electrohydraulic lithotripsy through a duodenal ulcer.

Video 1Crush the large-sized stones directly using an electrohydraulic lithotripsy device.

Size Control and Enhanced Stability of Silver Nanoparticles by Cyclic Poly(ethylene glycol).

Silver nanoparticles (AgNPs) are used in a wide range of applications, and the size control and stability of the nanoparticles are crucial aspects in their applications. In the present study, cyclized poly(ethylene glycol) (c-PEG) with various molecular weights, along with linear PEG with hydroxy chain ends (HO-PEG-OH) and methoxy chain ends (MeO-PEG-OMe) were applied for the Tollens' synthesis of AgNPs. The particle size was significantly affected by the topology and end groups of PEG. For example, the size determined by TEM was 40 ± 7 nm for HO-PEG5k-OH, 21 ± 4 nm for c-PEG5k, and 48 ± 9 nm for MeO-PEG5k-OMe when the molar ratio of PEG to AgNO3 (ω) was 44. The stability of AgNPs was also drastically improved by cyclization; the relative UV-Vis absorption intensity (A/A0 × 100%) at λmax to determine the proportion of persisting AgNPs in an aqueous NaCl solution (37.5 mM) was 58% for HO-PEG5k-OH, 80% for c-PEG5k, and 40% for MeO-PEG5k-OMe, despite the fact that AgNPs with c-PEG5k were much smaller than those with HO-PEG5k-OH and MeO-PEG5k-OMe.

PEGylation of silver nanoparticles by physisorption of cyclic poly(ethylene glycol) for enhanced dispersion stability, antimicrobial activity, and cytotoxicity.

Silver nanoparticles (AgNPs) are practically valuable in biological applications. However, no steady PEGylation has been established, which is essential for internal use in humans or animals. In this study, cyclic PEG (c-PEG) without any chemical inhomogeneity is physisorbed onto AgNPs to successfully PEGylate and drastically enhance the dispersion stability against physiological conditions, white light, and high temperature. In contrast, linear HO-PEG-OH and MeO-PEG-OMe do not confer stability to AgNPs, and HS-PEG-OMe, which is often used for gold nanoparticles, sulfidates the surface to considerably degrade the properties. TEM shows an essentially intact nanostructure of c-PEG-physisorbed AgNPs even after heating at 95 °C, while complete disturbance is observed for other AgNPs. Molecular weight- and concentration-dependent stabilization by c-PEG is investigated, and DLS and ζ-potential measurements prove the formation of a c-PEG layer on the surface of AgNPs. Furthermore, c-PEG-physisorbed AgNPs exhibit persistent antimicrobial activity and cytotoxicity.

Snare devices with thinner loop wire may provide higher performance for cold snare polypectomy in an experimental model.

Background and study aims Snare devices play an important role in treatment of intestinal polyps. However, there are no objective measurements for the characteristics of the various types of snare devices. Materials and methods Seven types of snare devices from four manufacturers were evaluated based on original measurements. The evaluated factors were stiffness, cutting quality, and change in force required for cutting depending on sheath shape. The latter two factors were evaluated by measuring the force required to cut 20 % gelatin cylinders, which simulated intestinal polyps. The cutting sharpness was evaluated by observing the sectional surface of cut gelatin cylinders using a stereomicroscope. The correlations between these measurements and characteristics of the snare devices were investigated. Results A strong positive correlation, with an R 2 value of 0.863, was shown between the force required to cut gelatin cylinders and loop wire diameter. Loop wire diameter also had a strong correlation, with an R 2 value of 0.7997, with the change in force required for cutting gelatin cylinders depending on sheath shape. No correlations were detected between loop stiffness and characteristics of snare devices. The edge-enhanced image revealed that the rougher surfaces of the gelatin cylinders were cut by snares with a thicker diameter. Conclusions Thinner loop wire may provide higher performance in cold snare polypectomy in an experimental model.

Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends.

The topology effects of cyclization on thermal phase transition behaviors were investigated for a series of amphiphilic Pluronic copolymers of both hydrophilic-hydrophobic-hydrophilic and hydrophobic-hydrophilic-hydrophobic block sequences. The dye solubilization measurements revealed the lowered critical micelle temperatures (TCMT) along with the decreased micellization enthalpy (ΔHmic) and entropy (ΔSmic) for the cyclized species. Furthermore, the transmittance and dynamic light scattering (DLS) measurements indicated a block sequence-dependent effect on the clouding phenomena, where a profound decrease in cloud point (Tc) was only found for the copolymers with a hydrophilic-hydrophobic-hydrophilic block sequence. Thus, the effect of cyclization on these critical temperatures was manifested differently depending on its block sequence. Finally, a comparison of the linear hydroxy-terminated, methoxy-terminated, and cyclized species indicated the effect of cyclization to be unique from a simple elimination of the terminal hydrophilic moieties.

Topology-Dependent Interaction of Cyclic Poly(ethylene glycol) Complexed with Gold Nanoparticles against Bovine Serum Albumin for a Colorimetric Change.

Unique physical and chemical properties arising from a polymer topology recently draw significant attention. In this study, cyclic poly(ethylene glycol) (c-PEG) was found to significantly interact with bovine serum albumin (BSA), suggested by nuclear magnetic resonance, dynamic light scattering, and fluorescence spectroscopy. On the other hand, linear HO-PEG-OH and MeO-PEG-OMe showed no affinity. Furthermore, a complex of gold nanoparticles and c-PEG (AuNPs/c-PEG) attracted BSA to form aggregates, and the red color of the AuNPs dispersion evidently disappeared, whereas ones with linear PEG or without PEG did not demonstrate such a phenomenon. The interactions among BSA, AuNPs, and PEG were investigated by changing the incubation time and concentration of the components by using UV-Vis and fluorescence spectroscopy.

Precise Synthesis and Thermoresponsive Property of Poly(ethyl glycidyl ether) and Its Block and Statistic Copolymers with Poly(glycidol).

In this paper, we describe a comprehensive study of the thermoresponsive properties of statistic copolymers and multiblock copolymers synthesized by poly(glycidol)s (PG) and poly(ethyl glycidyl ether) (PEGE) with different copolymerization methods. These copolymers were first synthesized by ring-opening polymerization (ROP), which was initiated by tert-butylbenzyl alcohol (tBBA) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylidenamino]-2Λ5,4Λ5-catenadi(phosphazene) (t-Bu-P4) as the catalyst, and then the inherent protective groups were removed to obtain the copolymers without any specific chain end groups. The thermoresponsive property of the statistic copolymer PGx-stat-PEGEy was compared with the diblock copolymer PGx-b-PEGEy, and the triblock copolymers were compared with the pentablock copolymers. Among them, PG-stat-PEGE, PG-b-PEGE-b-PG-b-PEGE-b-PG, and PEGE-b-PG-b-PEGE-b-PG-b-PEGE, and even the specific ratio of PEGE-b-PG-b-PEGE, exhibited LCST-type phase transitions in water, which were characterized by cloud point (Tcp). Although the ratio of x to y affected the value of the Tcp of PGx-stat-PEGEy, we found that the disorder of the copolymer has a decisive effect on the phase-transition behavior. The phase-transition behaviors of PG-b-PEGE, part of PEGE-b-PG-b-PEGE, and PG-b-PEGE-b-PG copolymers in water present a two-stage phase transition, that is, firstly LCST-type and then the upper critical solution temperature (UCST)-like phase transition. In addition, we have extended the research on the thermoresponsive properties of EGE homopolymers without specific α-chain ends.

Cyclization of PEG and Pluronic Surfactants and the Effects of the Topology on Their Interfacial Activity.

A series of cyclic surfactants were synthesized from a poly(ethylene glycol) (PEG) homopolymer and Pluronic surfactants L35, L64, P123, F68, 10R5, and 17R4, and their interfacial activity depending on the topology, chain ends, and block sequence was investigated. The cyclization was performed in a single step through etherification of the PEG homopolymer and the hydrophilic-hydrophobic-hydrophilic (ABA type) poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) (PEG-PPG-PEG), while the hydrophobic-hydrophilic-hydrophobic (BAB type) PPG-PEG-PPG was cyclized via acetalization. The cyclized surfactants were rigorously characterized by nuclear magnetic resonance spectroscopy and size exclusion chromatography. Cyclization of the surfactants induced a significant decrease in the hydrodynamic volume, which was more pronounced than that of the PEG homopolymer. Surface tension (γ) measurements indicated that the interfacial activity of the cyclized surfactants is stronger than their corresponding linear precursors, due to the increase in the surfactant density at the air-water interface as a consequence of the decreased molecular occupational area (A) upon cyclization. In the case of the PEG homopolymer, A considerably decreased from 410 Å2 for the linear PEG prepolymer to 100 Å2 for the cyclized PEG product. While the effects of chain-end groups were found to be limited to surfactants of relatively small molecular weights, the influence of cyclization depended strongly on the hydrophilic/hydrophobic ratio; the higher the PEG composition the surfactants had, the larger the decrease in γ and A; in other words, stronger enhancement in the interfacial activity was observed.

Molecular configuration-mediated thermo-responsiveness in oligo(ethylene glycol) derivatives attached on gold nanoparticles.

Biomolecular systems actively control their local environment on a sub-nm scale via changes in molecular configuration from their flexible structures and derive emergent functions. Although this functional emergence based on local environmental control is attracting a great deal of attention in chemistry, it remains challenging to realize this artificially. Herein, we report the tuning of the thermo-responsive properties of oligo(ethylene glycol) (OEG) derivatives attached on gold nanoparticles via local environmental control not only by the hydrophobic moiety at their terminus but also by their molecular configuration. OEG-attached alkane thiol-modified AuNPs showed thermo-responsive assembly/disassembly in water through the hydration/dehydration of the OEG portions in a manner dependent both on the hydrophobicity at their terminus and the surface curvature of the core nanoparticles. Further, the assembly temperature (T A) was also tuned by ligand mixing with a non-thermo-responsive ligand with a shorter OEG length. Molecular dynamics simulations show that the distribution of the hydrophobic terminus in the normal direction along the gold surface varied in accordance with the surface curvature, indicating variations in molecular configuration. It is expected that a bent configuration could accelerate the thermo-responsiveness of OEG by allowing them greater accessibility to the hydrophobic terminus. Experimental and simulation results support the notion that local OEG density tuning by surface curvature or ligand mixing with a different OEG length leads to different degrees of accessibility to the hydrophobic terminus via changes in molecular configuration, promoting local environmental control-directed assembly temperature tuning.

Tapering body stiffness shortens upper gastrointestinal examination via transoral insertion with ultrathin endoscope.

Background and study aims Ultrathin endoscopes are commonly used for surveillance esophagogastroduodenoscopy (EGD) to reduce discomfort associated with scope insertion. However, the flexibility of an ultrathin endoscope is a trade-off between reducing discomfort and lengthening examination time. Patients and methods The EG17-J10 (EG17) is a novel ultrathin endoscope characterized by its tapering body stiffness; however, the flexibility of its tip is comparable to that of the traditional ultrathin endoscope EG16-K10 (EG16). We compared EGD examination time between EG17 and EG16. A total of 319 examinees who underwent EGD from November 2019 to January 2020 at the Chiba-Nishi General Hospital were enrolled. Six examinees were excluded due to past history of surgical resection of the upper gastrointestinal tract or too much food residues; 313 examinees (EG17, 209; EG16,104) were retrospectively analyzed. The examination time was divided into three periods: esophageal insertion time (ET), gastroduodenal insertion time (GDT), and surveillance time of the stomach (ST). The total amount of ET, GDT, and ST was defined as total examination time (TT). Results TT of EGD using EG17 was significantly shorter compared to EGD using EG16 (222.7 ±â€Š68.9 vs. 245.7 ±â€Š78.5 seconds) ( P  = 0.004). Among the three periods of examination time, ET (66.7 ±â€Š24.1 vs. 76.0 ±â€Š24.1 seconds) ( P  = 0.001) and GDT (47.9 ±â€Š17.4 vs. 55.2 ±â€Š35.2 seconds) ( P  = 0.007) of EGD using EG17 were significantly shorter compared to EGD using EG16, except for ST (108.1 ±â€Š51.5.1 vs. 114.5 ±â€Š50.1 seconds) ( P  = 0.148). Conclusion An ultrathin endoscope with tapering body stiffness can shorten EGD examination time, mainly due to the shortening of insertion time.

Enhanced dispersion stability of gold nanoparticles by the physisorption of cyclic poly(ethylene glycol).

Nano-sized metal particles are attracting much interest in industrial and biomedical applications due to the recent progress and development of nanotechnology, and the surface-modifications by appropriate polymers are key techniques to stably express their characteristics. Herein, we applied cyclic poly(ethylene glycol) (c-PEG), having no chemical inhomogeneity, to provide a polymer topology-dependent stabilization for the surface-modification of gold nanoparticles (AuNPs) through physisorption. By simply mixing c-PEG, but not linear counterparts, enables AuNPs to maintain dispersibility through freezing, lyophilization, or heating. Surprisingly, c-PEG endowed AuNPs with even better dispersion stability than thiolated PEG (HS-PEG-OMe). The stronger affinity of c-PEG was confirmed by DLS, ζ-potential, and FT-IR. Furthermore, the c-PEG system exhibited prolonged blood circulation and enhanced tumor accumulation in mice. Our data suggests that c-PEG induces physisorption on AuNPs, supplying sufficient stability toward bio-medical applications, and would be an alternative approach to the gold-sulfur chemisorption.

Hexagonal boron nitride: a review of the emerging material platform for single-photon sources and the spin-photon interface.

Single-photon sources and their optical spin readout are at the core of applications in quantum communication, quantum computation, and quantum sensing. Their integration in photonic structures such as photonic crystals, microdisks, microring resonators, and nanopillars is essential for their deployment in quantum technologies. While there are currently only two material platforms (diamond and silicon carbide) with proven single-photon emission from the visible to infrared, a quantum spin-photon interface, and ancilla qubits, it is expected that other material platforms could emerge with similar characteristics in the near future. These two materials also naturally lead to monolithic integrated photonics as both are good photonic materials. While so far the verification of single-photon sources was based on discovery, assignment and then assessment and control of their quantum properties for applications, a better approach could be to identify applications and then search for the material that could address the requirements of the application in terms of quantum properties of the defects. This approach is quite difficult as it is based mostly on the reliability of modeling and predicting of color center properties in various materials, and their experimental verification is challenging. In this paper, we review some recent advances in an emerging material, low-dimensional (2D, 1D, 0D) hexagonal boron nitride (h-BN), which could lead to establishing such a platform. We highlight the recent achievements of the specific material for the expected applications in quantum technologies, indicating complementary outstanding properties compared to the other 3D bulk materials.

Switching of Fluorescent Zn/Cd Selectivity in N,N,N',N'-Tetrakis(6-methoxy-2-quinolylmethyl)-1,2-diphenylethylenediamine by One Asymmetric Carbon Atom Inversion.

A quinoline-based hexadentate ligand, (S,S)-N,N,N',N'-tetrakis(6-methoxy-2-quinolylmethyl)-1,2-diphenylethylenediamine ((S,S)-6-MeOTQPh2EN), exhibits fluorescence enhancement at 498 nm upon addition of 1 equiv of Zn2+ (IZn/I0 = 12, φZn = 0.047) in aqueous DMF solution (DMF/H2O = 2:1). Addition of 1 equiv of Cd2+ affords a much smaller fluorescence increase at the same wavelength (ICd/I0 = 2.5, ICd/IZn = 21%). The trivalent metal ions such as Al3+, Cr3+, and Fe3+ also exhibit fluorescence enhancement at 395 nm (IAl/I0 = 22, ICr/I0 = 6 and IFe3+/I0 = 13). In contrast, meso-6-MeOTQPh2EN exhibits a Cd2+-selective fluorescence increase at 405 nm in the presence of 1 equiv of metal ion (ICd/I0 = 11.5, φCd = 0.022), while Zn2+ induces a smaller fluorescent response under the same experimental conditions (IZn/I0 = 3.3, IZn/ICd = 29%). In this case, the fluorescence intensities of meso-6-MeOTQPh2EN in the presence of a large amount of Zn2+ and Cd2+ become similar. This diastereomer-dependent, fluorescent metal ion specificity is derived from the Zn2+-specific intramolecular excimer formation in (S,S)-6-MeOTQPh2EN-Zn2+ complex and higher binding affinity of meso-6-MeOTQPh2EN with Cd2+ in comparison to Zn2+. The more conformationally restricted diastereomeric pair, namely, cis- and trans-TQDACHs (cis- and trans-N,N,N',N'-tetrakis(2-quinolylmethyl)-1,2-diaminocyclohexanes), both exhibit Zn2+-specific fluorescence enhancement because of the high metal binding affinity and intramolecular excimer forming property derived from the rigid DACH backbone.

A case of a rectal adenocarcinoma mimicking a neuroendocrine tumor in the background mucosa of amoebic colitis.

A 54-year-old man with diarrhea and hematochezia for 2 months was referred to our department. A total colonoscopy revealed amoebic colitis caused by Entamoeba histolytica. Concurrently, a submucosal tumor-like yellowish hemispheric polypoid lesion was incidentally detected in the rectum. We speculated that the lesion was a NET, which could be cured by endoscopic treatment. However, histopathological assessment of a biopsy specimen unexpectedly revealed a well- or moderately differentiated adenocarcinoma. After treatment of the amoebic colitis, endoscopic ultrasound revealed a low, hetero-echoic, 6-mm-diameter lesion mainly in the submucosal layer. We performed surgical resection because the invasion was estimated to be to the deeper submucosal layer. Histopathological assessment of the surgically resected specimen revealed a focal lesion of a well-differentiated adenocarcinoma in the granulation tissue of the submucosal layer. In cases accompanied by amoebic colitis, a tumor's initial gross type might change. Diagnostic endoscopic resection could be acceptable in such cases.

Deterministic placement of ultra-bright near-infrared color centers in arrays of silicon carbide micropillars.

We report the enhancement of the optical emission between 850 and 1400 nm of an ensemble of silicon mono-vacancies (VSi), silicon and carbon divacancies (VCVSi), and nitrogen vacancies (NCVSi) in an n-type 4H-SiC array of micropillars. The micropillars have a length of ca. 4.5 µm and a diameter of ca. 740 nm, and were implanted with H+ ions to produce an ensemble of color centers at a depth of approximately 2 µm. The samples were in part annealed at different temperatures (750 and 900 °C) to selectively produce distinct color centers. For all these color centers we saw an enhancement of the photostable fluorescence emission of at least a factor of 6 using micro-photoluminescence systems. Using custom confocal microscopy setups, we characterized the emission of VSi measuring an enhancement by up to a factor of 20, and of NCVSi with an enhancement up to a factor of 7. The experimental results are supported by finite element method simulations. Our study provides the pathway for device design and fabrication with an integrated ultra-bright ensemble of VSi and NCVSi for in vivo imaging and sensing in the infrared.