Modular Synthetic Platform for Interior-Functionalized Dendritic Macromolecules Enabled by the Palladium/Norbornene Catalysis.

Synthesis of interior-functionalized dendritic macromolecules is generally tedious and labor-intensive, which has been a key factor hampering their practical applications. Here, we have revisited this long-standing challenge and devised a modular and convergent platform to synthesize multifunctional dendrons with all-carbon backbones up to four generations via an in situ functionalization strategy. Enabled by the palladium/norbornene cooperative catalysis, different functional groups can be introduced to each generation of dendrons during the dendron growth, making it convenient for systematic comparison of their properties. The utility of this versatile platform is further showcased in the internal-functionalization-dependent properties of dendrons as organogels and aggregation-induced emission materials.

Comparative Study of the Morphology of Cellulose Nanofiber Fabricated Using Two Kinds of Grinding Method.

In this paper, a comparison of cellulose nanofiber (CNF) fabrication from Gelidium amansii using two kinds of grinding processes is presented. The cellulose from Gelidium amansii is pretreated with hydrogen peroxide and sodium carbonate in a separating and bleaching process. Then, two grinding processes (method A and B) are used to fabricate CNFs. The first is a traditional method of fabricating CNFs using a disc grinder, whereas the second method is identical to the first, but includes an additional step involving a planetary ball mill. In the new method (method B), dry cellulose powder is prepared using a planetary ball mill, which has the advantage of long-term storage and maintains the original quality of the cellulose. The morphological changes of the dry cellulose powder and CNFs are determined using scanning electron microscopy and field emission scanning electron microscopy. The physical characteristics of the CNFs are found to be significantly different when we change the disc grinder used in the grinding method to produce nanometer scale where the best result is homogeneous, uniform CNFs with a fabricated width of 19 nm.

Scalable and continuous access to pure cyclic polymers enabled by 'quarantined' heterogeneous catalysts.

Cyclic polymers are topologically interesting and envisioned as a lubricant material. However, scalable synthesis of pure cyclic polymers remains elusive. The most straightforward way is to recover a used catalyst after the synthesis of cyclic polymers and reuse it. Unfortunately, this is demanding because of the catalyst's vulnerability and inseparability from polymers, which reduce the practicality of the process. Here we develop a continuous circular process, where polymerization, polymer separation and catalyst recovery happen in situ, to dispense a pure cyclic polymer after bulk ring-expansion metathesis polymerization of cyclopentene. It is enabled by introducing silica-supported ruthenium catalysts and newly designed glassware. Different depolymerization kinetics of the cyclic polymer from its linear analogue are also discussed. This process minimizes manual labour, maximizes the security of vulnerable catalysts and guarantees the purity of cyclic polymers, thereby showcasing a prototype of a scalable access to cyclic polymers with increased turnovers (≥415,000) of precious catalysts.

Semen evaluation: methodological advancements in sperm quality-specific fertility assessment - A review.

Assessment of male fertility is based on the evaluation of sperm. Semen evaluation measures various sperm quality parameters as fertility indicators. However, semen evaluation has limitations, and it requires the advancement and application of strict quality control methods to interpret the results. This article reviews the recent advances in evaluating various sperm-specific quality characteristics and methodologies, with the help of different assays to assess sperm-fertility status. Sperm evaluation methods that include conventional microscopic methods, computer-assisted sperm analyzers (CASA), and flow cytometric analysis, provide precise information related to sperm morphology and function. Moreover, profiling fertility-related biomarkers in sperm or seminal plasma can be helpful in predicting fertility. Identification of different sperm proteins and diagnosis of DNA damage has positively contributed to the existing pool of knowledge about sperm physiology and molecular anomalies associated with different infertility issues in males. Advances in methods and sperm-specific evaluation has subsequently resulted in a better understanding of sperm biology that has improved the diagnosis and clinical management of male factor infertility. Accurate sperm evaluation is of paramount importance in the application of artificial insemination and assisted reproductive technology. However, no single test can precisely determine fertility; the selection of an appropriate test or a set of tests and parameters is required to accurately determine the fertility of specific animal species. Therefore, a need to further calibrate the CASA and advance the gene expression tests is recommended for faster and field-level applications.

Multicomponent Polymerization for π-Conjugated Polymers.

Structurally complex π-conjugated polymers hold great promise as key components in sensor and electronic devices; however, their syntheses have not been a trivial task. From a synthetic efficiency perspective, it would be more attractive to access these materials using convenient and efficient methods from simple building blocks. One such synthetic tool, multicomponent polymerization, can accommodate modularity and provide highly efficient syntheses. This feature article outlines several multicomponent polymerization strategies for the synthesis of various π-conjugated polymers, which are classified based upon how the monomers are aligned during polymerization. Additionally, the challenges and outlooks of this field are highlighted and discussed.

Sulfenamide-enabled ortho thiolation of aryl iodides via palladium/norbornene cooperative catalysis.

Poly-substituted aromatic sulfur compounds are widely found in pharmaceuticals, agrochemicals and organic materials. However, the position that a sulfur moiety can be introduced to is largely restricted to a pre-functionalized site; otherwise, use of electronically biased substrates or auxiliary groups that direct catalysis is required. Here we report a general ortho thiolation of common aryl and heteroaryl iodides via palladium-norbornene cooperative catalysis. Using this approach, an aryl or alky sulfur moiety can be site-selectively introduced at the arene ortho position without using sterically or electronically biased substrates. The arene ipso functionalization is simultaneously achieved through Heck, Suzuki or Sonogashira termination. The reaction is enabled by a unique class of electrophiles in palladium-norbornene cooperative catalysis, which are sulfenamides derived from seven-membered lactams. The broad substrates scope and high chemoselectivity could make this method attractive for synthesis of complex sulfur-containing aromatic compounds.

Modular In†Situ Functionalization Strategy: Multicomponent Polymerization by Palladium/Norbornene Cooperative Catalysis.

Herein, we report a cooperatively palladium/norbornene-catalyzed polymerization, which simplifies the synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2 B2 C-type multicomponent polymerization that is based on an ortho amination/ipso alkynylation reaction was developed for the preparation of various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side chains are site-selectively installed in situ by C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This "in situ functionalization" strategy enables the modular incorporation of functional side chains starting from simple monomers, thereby conveniently affording a diverse range of functional polymers.

A modular synthetic approach for band-gap engineering of armchair graphene nanoribbons.

Despite the great promise of armchair graphene nanoribbons (aGNRs) as high-performance semiconductors, practical band-gap engineering of aGNRs remains an unmet challenge. Given that width and edge structures are the two key factors for modulating band-gaps of aGNRs, a reliable synthetic method that allows control of both factors would be highly desirable. Here we report a simple modular strategy for efficient preparation of N = 6 aGNR, the narrowest member in the N = 3p (p: natural number) aGNR family, and two unsymmetrically edge-functionalized GNRs that contain benzothiadiazole and benzotriazole moieties. The trend of band-gap transitions among these GNRs parallels those in donor-acceptor alternating conjugated polymers. In addition, post-functionalization of the unsymmetrical heterocyclic edge via C-H borylation permits further band-gap tuning. Therefore, this method opens the door for convenient band-gap engineering of aGNRs through modifying the heteroarenes on the edge.

Postoperative oral nutritional supplementation after major gastrointestinal surgery: a randomized controlled clinical trial.

BACKGROUND AND OBJECTIVES: This study aimed to evaluate the efficacy of post-operative oral nutrition supplementation after major gastrointestinal surgery. METHODS AND STUDY DESIGN: A prospective randomized controlled trial was conducted to evaluate 174 subjects who were discharged within 2 weeks after major gastrointestinal surgery. The subjects in the study group were prescribed 400 ml/day of Encover® from the day of discharge for 8 weeks, but no supplementation was allowed in the control group. The primary endpoint was the weight loss rate at 8 weeks after discharge compared with the pre-operative weight, and the secondary endpoints included changes in body weight, body mass index, Patient-Generated Subjective Global Assessment score/grade, hematological/ biochemical parameters, and adverse events evaluated at 2, 4, and 8 weeks after discharge. RESULTS: The weight loss rate at 8 weeks after discharge did not differ between two groups (4.23±5.49% vs 4.80±4.84%, p=0.481). The total lymphocyte count, the level of total cholesterol, total protein, and albumin were significantly higher in the study group after discharge. Diarrhea was the most frequent adverse event, and the incidence of adverse events with a severity score of >=3 did not differ between groups (2.3% vs 1.2%). CONCLUSIONS: The utility of routine oral nutritional support after major gastrointestinal surgery was not proven in terms of weight loss at 8 weeks after discharge. However, it can be beneficial for early recovery of biochemical parameters.

Genome characteristics of the proteorhodopsin-containing marine flavobacterium Polaribacter dokdonensis DSW-5.

Bacteria in the genus Polaribacter, belonging to the family Flavobacteriaceae, are typically isolated from marine environments. Polaribacter dokdonensis DSW-5, the type strain of the species, is a Gram-negative bacterium isolated from the East Sea of Korea. Whole genome shotgun sequencing was performed with the HiSeq 2000 platform and paired-end reads were generated at 188-fold coverage. The sequencing reads were assembled into two contigs with a total length of 3.08 Mb. The genome sequences of DSW-5 contain 2,776 proteincoding sequences and 41 RNA genes. Comparison of average nucleotide identities among six available Polaribacteria genomes including DSW-5 suggested that the DSW-5 genome is most similar to that of Polaribacter sp. MED152, which is a proteorhodopsin-containing marine bacterium. A phylogenomic analysis of the six Polaribacter strains and 245 Flavobacteriaceae bacteria confirmed a close relationship of the genus Polaribacter with Tenacibaculum and Kordia. DSW-5's genome has a gene encoding proteorhodopsin and genes encoding 85 enzymes belonging to carbohydrate-active enzyme families and involved in polysaccharide degradation, which may play important roles in energy metabolism of the bacterium in the marine ecosystem. With genes for 238 CAZymes and 203 peptidases, DSW-5 has a relatively high number of degrading enzymes for its genome size suggesting its characteristics as a free-living marine heterotroph.

Efficient Bottom-Up Preparation of Graphene Nanoribbons by Mild Suzuki-Miyaura Polymerization of Simple Triaryl Monomers.

Herein an efficient bottom-up solution-phase synthesis of N=9 armchair graphene nanoribbons (GNRs) is described. Catalyzed by Pd(PtBu3 )2 , Suzuki-Miyaura polymerization of a simple and readily available triaryl monomer provides a novel GNR precursor with a high molecular weight and excellent solubility. Upon cyclodehydrogenation, the resulting GNR exhibits semiconducting properties with an approximately 1.1 eV band gap (LUMO: -3.52 eV; HOMO: -4.66 eV) as characterized by UV/Vis-NIR spectroscopy and cyclic voltammetry.

Transgenesis for pig models.

Animal models, particularly pigs, have come to play an important role in translational biomedical research. There have been many pig models with genetically modifications via somatic cell nuclear transfer (SCNT). However, because most transgenic pigs have been produced by random integration to date, the necessity for more exact gene-mutated models using recombinase based conditional gene expression like mice has been raised. Currently, advanced genome-editing technologies enable us to generate specific gene-deleted and -inserted pig models. In the future, the development of pig models with gene editing technologies could be a valuable resource for biomedical research.

One-pot preparation of 3D nano- and microaggregates via in situ nanoparticlization of polyacetylene diblock copolymers produced by ROMP.

Zero-dimensional (0D) nanospheres, 1D nanocaterpillars, and 3D aggregates are produced from simple diblock copolymers containing polyacetylene (PA) via in situ nanoparticlization of conjugated polymers. The diblock copolymers are prepared by ring-opening metathesis polymerization via one-pot sequential addition of an endo-tricyclo[4.2.2.0]deca-3,9-diene (TD) and cyclooctatetraene. Initially, they spontaneously form nanospheres consisting of a PA core and PTD shell, and increasing the length of the PA block leads to the direct nanoparticlization of the higher-dimensional structures such as 1D and 3D aggregates because of the decreased effective volume ratio of the rigid PTD shell to the solvophobic PA core.

Nanostar and nanonetwork crystals fabricated by in situ nanoparticlization of fully conjugated polythiophene diblock copolymers.

Nanostar and nanonetwork crystals were prepared from fully conjugated poly(3-(2-ethylhexyl)thiophene)-block-polythiophene (P3EHT-b-PT) via a simple INCP process. The structural conformation of the nanocrystals was investigated in detail, revealing that with an increase in the block length of PT, the morphology of the nanocrystals changed from nanospheres to nanorods, nanostars, and to nanonetworks.

One-pot in situ fabrication of stable nanocaterpillars directly from polyacetylene diblock copolymers synthesized by mild ring-opening metathesis polymerization.

We report a direct one-pot route for the preparation of supramolecules from simple polyacetylene diblock copolymers synthesized by mild ring-opening metathesis polymerization of cyclooctatetraene. This in situ nanoparticlization of conjugated polymer (INCP) approach is advantageous over conventional self-assembly processes because this method does not require any tedious postsynthetic treatments. Also, this direct approach provides intriguing supramolecules with a unique nanostructure resembling a caterpillar. Furthermore, the new supramolecules are highly stable adducts because the polyacetylene core block provides an exceptionally strong driving force for the self-assembly. Even though pristine polyacetylene is unstable in air, the polyacetylene segment in the nanocaterpillar is very stable because it is protected within the shell of the supramolecule.

A case of metastatic leptomeningeal carcinomatosis from early gastric carcinoma.

Metastatic leptomeningeal carcinomatosis is estimated to occur in 3% to 8% of solid carcinomas. The most common causes of leptomeningeal carcinomatosis are breast cancer, lung cancer and malignant melanoma. Leptomeningeal carcinomatosis associated with gastric cancer, especially in its early stages, is exceedingly rare. Its presenting symptoms include headache, nausea and seizures. In this report, we describe a case of leptomeningeal metastasis that presented with early-stage gastric cancer. A 67-year-old woman with a history of early-stage gastric cancer in remission was admitted to our hospital with 3 days of headache and nausea. Her gastric cancer had been treated 29 months prior to presentation by a radical subtotal gastrectomy with a Billroth I anastomosis. She had an uneventful recovery until she was diagnosed with metastases to the left axilla and neck 26 months after surgery. Her presenting symptoms of headache and nausea prompted cytologic examination of the cerebrospinal fluid and measurement of tumor markers, which revealed metastatic leptomeningeal carcinomatosis from her gastric cancer. This report aims to raise awareness of the possibility that even early-stage gastric cancer can lead to leptomeningeal carcinomatosis.

Susceptibility constants of Escherichia coli and Bacillus subtilis to silver and copper nanoparticles.

Nanoparticle susceptibility constants were defined and used to evaluate the antimicrobial characteristics of silver and copper nanoparticles against Escherichia coli and Bacillus subtilis. Reaction of copper nanoparticles of 100 nm with B. subtilis showed the highest susceptibility (Z=0.0734 mL/microg) whereas the reaction of silver nanoparticles of 40 nm with E. coli showed the lowest one (Z=0.0236 mL/microg).