Propylene carbonate

The concentration of Texas Red (TxRed) labeled HER2 DNA probe (size 218 kb) was 3.3 ng/µL and of fluorescein labeled CEN-17 peptide nucleic acid (PNA) oligo probe, 250 nM (Dako) [15] . The concentration of 20×HER2 DNA used in Figure S7A + S7B was 67.1 ng/µL. The TxRed labeled BCL2 DNA probe (size 375 kb, telomeric to the major breakpoint region) was 7.3 ng/µL and fluorescein labeled BCL2 DNA probe (size 641 kb, centromeric to the major breakpoint cluster region) was 12.9 µg/µL (Dako) [16] (link).
The solvents: ethylene carbonate (E26258), sulfolane (T22209), propylene carbonate ((540013), γ-butyrolactone (B103608), 2-pyrrolidone (240338) and δ-valerolactam (V209) were from Sigma-Aldrich (Copenhagen, Denmark). Formamide was from Invitrogen, Nærum, Denmark (15515-026).
The 15% solvent and formamide buffers consisted of: 15% v/v solvent or formamide; 20% v/v dextran sulfate (D8906, Sigma-Aldrich); 600 mM NaCl; 10 mM citrate buffer; pH 6.2.
The 45% formamide and solvent buffer consisted of: 45% v/v formamide or solvent; 10% v/v dextran sulfate; 0.1 µg/µL Human Cot-1 (15279-011, Invitrogen); 300 mM NaCl; 5 mM phosphate buffer; pH 7.5. The 45% formamide 20×DNA buffer had no Cot-1 added in Figure S7a.

To measure strain and stress without changing the test setup, a Linear Actuation Staging (LAS) with an isometric transducer (force sensor) were combined. The setup is shown in Figure 1a and the connection hierarchy in Figure 1b.
Figure 1a shows that the sample (6) is attached between two clamps. The lower clamp is static and is fixed to the chassis (1) of the LAS (Linear actuation stage). The upper clamp is attached to a force sensor (7) which is mounted on a plate of the LAS (Physik instrumente M-414.3PD, min step size 0.5 µm, Karlsruhe, Germany) that enables it to perform linear movements. Figure 1b shows the hierarchy of the devices. The signal of the force sensor (Panlab TRI202PAD, Barcelona, Spain) is read by a voltmeter (Keithley 2182A, Beaverton, United States) which exchanges data with the computer over a General-Purpose Interface Bus (GPIB) to Universal Serial Bus (USB) converter (Prologix Rev 6.4.1, Asheville, North Carolina). The LAS (Physik Instrumente M-414.3PD, Karlsruhe, Germany) is controlled by a controller (Physik Instrumente C-863, Karlsruhe, Germany), which accepts commands from the computer via a serial port. Lastly, the potentiostat (Biologic PG581, Göttingen, Germany) is connected to the computer using a USB interface.
To examine the samples, PPy/DBS films and MWCNT-CDC fibers were cut in strips of 1.0 cm * 0.1 cm and fixed between the force sensor and on the fixed arm with gold contacts that served as a working electrode in the linear muscle analyzer setup (Figure 1). The initial length of the films between the clamps was 1 mm. The strain, ε, was calculated from the formula ε = Δl/l, where Δl refers to l –l₁ with l as the original length of the film (1 mm) and l₁ the change of length obtained from isotonic measurements. The load applied on PPy/DBS films was 6 g (58.8 mN, 3.2 MPa) and the load on MWCNT-CDC films was 60 mg (0.6 mN, 33.2 kPa). For isometric (force) measurements, the stress, σ, was calculated using the formula σ = F/A, where F is the force in N acting on an object (F = m*g with m the mass and g means acceleration due to gravity as a constant 9.8 m s⁻²) and A represents the cross-sectional area of the object (width * thickness). A platinum sheet was used as the counter electrode in the measurements cell and Ag/AgCl (3M KCl) as the reference electrode. For PPy/DBS films and for MWCNT-CDC fibers, 0.2 M LiTFSI propylene carbonate solution was applied. For isotonic and isometric measurements, cyclic voltammetry (scan rate 5 mV s⁻¹) was used for driving in the potential range of 0.65 to −0.6 V.

PPy/DBS was polymerized galvanostatically at 0.1 mA cm⁻² (40,000s) in a 2-electrode cell with a stainless-steel mesh counter electrode and a stainless-steel sheet working electrode (18 cm²) in a 0.1 M NaDBS, 0.1 M Py, in EG/Milli-Q (1:1) mixture. The temperature of the polymerization was −40 °C. The obtained PPy/DBS films were washed in ethanol to remove excess of pyrrole with additional washing steps in MilliQ+ water to remove excess of NaDBS, and dried in an oven. The film, in thickness of 18.5 µm, were then stored in LiTFSI propylene carbonate (0.2 M) electrolyte.

ExperimentalPhthalimide (99%) and propylene carbonate (99%) were purchased from Alfa Aesar. 1(2H)-Phthalazinone (99%), 4(3H)-pyrimidone (98%), 2,4-dihydroxy-6-methylpyrimidine (97%) and propylene carbonate (99.7%) were purchased from Sigma-Aldrich. Isatin (98%) was purchased from Reanal, 1H-benzotriazole (99%) was purchased from Merck, 2-thiouracil (98%) was purchased from Fluka, sodium carbonate (99.5%) was purchased from Acidum and calcium chloride (98.1%) was purchased from Molar.
Thin-layer chromatography (TLC) was performed on aluminium sheets precoated with Merck 5735 Kieselgel 60F254 (Merck, Darmastadt). Column chromatography was carried out with Merck 5735 Kieselgel 60F (0.040–0.063 nm mesh). All other chemicals and solvents were purchased from different commercial sources and used as received without further purification.
Freeze-drying was performed one night in a LYPH-Lock 1L lyophiliser LabConco (Kansas City, MI, USA) with a high vacuum pump at 10 mmHg and −50 °C. Melting points were measured on a Büchi M-550 apparatus (Büchi Labortechnik AG, Flawil, Switzerland) and are not corrected.
ProceduresMethod A: Reaction under oil bath (with 99% PC and drying agent)The substrate (4 mmol of 1, 2, 4, 5, 6 or 7, except for 3: 3 mmol), the solid Na₂CO₃ (4 mmol in the case of 1, 2, 4, 5, 6 or 7, except for 3: 3 mmol), the drying agent CaCl₂ (4 mmol in the case of 1, 2, 4, 5, 6 or 7, except for 3: 3 mmol) and 99% propylene carbonate (36 mmol, 3 mL, d = 1.204 g/mL in the case of 1, 2, 3, 4, 6 or 7, except for 5: 48 mmol, 4 mL, d = 1.204 g/mL) were measured into a round-bottom flask with a Liebig-condenser and gas-outlet adapter and the suspension was treated at reflux temperature at a max. oil bath temperature of 170 °C. After the different reaction time (Tables S2–S8), the suspension was cooled down and the unreacted solid filtered off. After washing with water, the mother liquid was neutralised with 10% HCl solution and the aqueous layer was extracted with CHCl₃ (3 × 25 mL, in the case of 2, 5) and EtOAc (3 × 25 mL, in the case of 1, 3, 4, 6, 7), respectively. Usually, the organic phase contained the product (10, 11, 12, 16 and 17), but in some cases, the extraction was satisfactory only to separate the unreacted propylene carbonate and propylene glycol from the raw product, which remained in the neutralised aqueous phase (product 8, 9, 13, 14, 15, 18 and 19). The collected organic phase was washed with 10% CuSO₄ solution (2 × 15 mL) and evaporated after drying over Na₂SO₄ and filtration. In each case, the crude product was lyophilised overnight at 10 mmHg and −50 °C and weighted before the product was purified by column chromatography (silica gel, 0.040–0.063 mesh size, except product 10, obtained after treatment with hexane). The unsuccessful reactions are not described in detail, but some are mentioned in Tables S2 and S3. All pure products—8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 and 19—were characterised by ¹H-, ¹³C-NMR spectroscopy and HPLC-MS.
Method B: Reactions under MW conditions (with and without drying agent)MW-assisted experiments were carried out in a monomode CEM-Discover MW reactor using the standard configuration as delivered, including proprietary software. The experiments were executed in 80 mL MW process vials, a dynamic method with control of the temperature by infrared detection. Conditions: 5 min. ramp time, 150 °C temperature, different hold time, max. 200 Psi pressure and 300 W power. The amount of reagents was identical to that used in Method A; however, in spite of that, the use of drying agent was not necessary when 99.7% PC was the reagent and solvent too. After the corresponding reaction time (Tables S2–S8), the vial was cooled to 50 °C by air jet cooling, followed by the usual work-up, described in Method A.
Structure characterisation data:
72 mg (11%) yellowish oil 1-(2-hydroxypropyl)pyrimidine-2,4(1H,3H)-dione (16), C₇H₁₀N₂O₃: 170.17, CAS Reg. No: 1479918-99-4, Rf = 0.40 (CHCl₃/MeOH 5/1), rt = 0.23′ (94%), m/z = 171.
¹H NMR (400 MHz, DMSO-d₆): δ = 1.04 (d, J = 6.2 Hz, 3H, CH₃), 3.38 (dd, J = 13.6, 8.4 Hz, 1H, CH₂), 3.71 (dd, J = 13.6, 3.6 Hz, 1H, CH₂), 3.82 (m, 1H, CHOH), 5.49 (d, J = 7.8 Hz, 1H, O=CCH), 7.52 (d, J = 7.8 Hz, 1H, NCH).
¹³C NMR (100 MHz, DMSO-d₆): δ = 20.7, 54.5, 64.0, 100.0, 146.9, 151.3, 164.1.
42 mg (5%) white oily solid 1,3-bis(2-hydroxypropyl)pyrimidine-2,4(1H,3H)-dione (17), C₁₀H₁₆N₂O₄: 228.25, Rf = 0.55 (CHCl₃/MeOH 5/1), rt = 0.22′ (100%), m/z = 229.
¹H NMR (400 MHz, DMSO-d₆): δ = 1.00 (d, J = 6.0 Hz, 3H, N³CH₂CHCH₃), 1.05 (d, J = 6.2 Hz, 3H, N¹CH₂CHCH₃), 3.44 (m, 1H, N¹CH₂), 3.66 (m, 1H, N³CH₂), 3.77 (m, 1H, N¹CH₂), 3.84 (m, 1H, N³CH₂), 3.83 (m, 1H, N¹CH₂CH), 3.89 (m, 1H, N³CH₂CH), 4.67 (d, J = 5.2 Hz, 1H, N³CH₂CHOH), 4.93 (d, J = 4.8 Hz, 1H, N¹CH₂CHOH) 5.63 (d, J = 7.8 Hz, 1H, O=CCH), 7.54 (d, J = 7.8 Hz, 1H, NCH).
¹³C NMR (100 MHz, DMSO-d₆): δ = 20.7, 21.1, 47.1, 55.7, 63.3, 64.0, 99.4, 145.3, 151.5, 162.9.

Acryloyl chloride (96%, Alfa Aesar, Ward Hill, MA, USA), 5-bromo-1-pentanol (>95%, TCI, Tokyo, Japan), 6-bromo-1-hexanol (>95%, TCI), 10-bromo-1-decanol (>95%, TCI), 1-ethylimidazole (>98%, TCI), magnesium sulfate (MgSO₄, >98%, Sigma Aldrich, St. Louis, MO, USA), silver nitrate (AgNO₃, 0.1 M, Sigma Aldrich), triethylamine (TEA, 99%, Alfa Aesar, Haverhill, MA, USA), a,a′-azobis(isobutyronitrile) (AIBN), and poly(propylene carbonate) (PPC, Mw = 50,000 g/mol, Sigma Aldrich) were used as received. Lithium bis(trifluoromethane sulfonyl)imide (LiTFSI, 99%, IoLiTec Ionic Liquids Technologies GmbH, Heilbronn, Germany) was dried under vacuum at 110 °C for 24 h prior the use, separator Cellgard 2500 (Celgard LLC, Charlotte, NC, USA).

Propylene carbonate (PC, Chloroform solution of 6% propylene carbonate) was used to pick up boron nitride (h-BN) that has been mechanically exfoliated onto silicon oxide. The picked h-BN was dropped onto the as-grown MoS₂ to pick up the single crystal MoS₂. Then, two parallel graphene samples were picked up as contact electrodes. Finally, the sample falls onto bulk h-BN on 300-nm silicon oxide substrate to obtain van der Waals heterojunction with clean interface and free of organic residues.